Method of colouring porous material

ABSTRACT

A method of colouring porous material, especially human hair, is described, which method comprises applying to the material being coloured, in any desired order successively, or simultaneously, a) at least one capped diazonium compound of Formula (1) and/or at least one compound of Formula (2) and/or at least one compound of Formula (3) wherein Q is an unsubstituted or substituted aromatic or heterocyclic residue, R is the radical of an unsubstituted or substituted, water-soluble aliphatic or aromatic amine, and T is an unsubstituted or substituted, water-soluble aliphatic or aromatic residue, wherein at least one of the groups must contain a radical imparting water solubility, and a) at least one water-soluble coupling component under conditions such that, initially, coupling does not take place, and then causing the capped diazonium compound present on the material to react with the coupling component.

The present invention relates to a method of colouring porous material,for example metal, wood or keratin-containing fibres, especially humanhair, using developing dyes, that is to say dyes which are formed insidethe pores of the substrate.

Colouring with the aid of developing dyes has been known for a long timeand has also been generally used for dyeing cotton. The dyes and thecolouring methods used therefore do not, however, provide satisfactoryresults for colouring hair.

For colouring hair, therefore, oxidation dyes are used in most cases;however, they too are not capable of satisfying all requirements. Thefastness to washing properties are often inadequate and, in addition,the colouring conditions required often cause a greater or lesser amountof damage to the hair. There has therefore been a need for a colouringmethod which does not have the mentioned disadvantages or which has themto an insignificant degree.

The present invention relates to a method of colouring porous material,which comprises applying to the material being coloured, in any desiredorder successively, or simultaneously,

-   a) at least one capped diazonium compound and-   b) at least one water-soluble coupling component    under conditions such that, initially, coupling does not take place,    and then causing the capped diazonium compound present on the    material to react with the coupling component.

The colorations obtained are distinguished by outstanding fastness towashing properties, which are significantly better than in the case ofcolorations with oxidation dyes, and there is virtually no damage to thehair. Moreover, there is no staining of the scalp, because the dyecomponents do not penetrate into the skin and non-fixed dye can bewashed off readily.

Suitable capped diazonium compounds include, for example, compounds offormula (1) compounds of formula (2)

and compounds of formula (3)

wherein

-   Q is an unsubstituted or substituted aromatic or heterocyclic    residue,-   R is the radical of an unsubstituted or substituted, water-soluble    aliphatic or aromatic amine, and-   T is an unsubstituted or substituted, water-soluble aliphatic or    aromatic residue,-   wherein at least one of the groups must contain a radical imparting    water solubility.

Suitable radicals imparting water solubility include, for example, SO₃H,COOH or OH.

Q is an unsubstituted or substituted aromatic or heterocyclic residue.For example, unsubstituted or substituted phenyl, naphthyl, thiophenyl,1,3-thiazolyl, 1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl,Imidazolyl, 1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl,pyrazolyl, benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl,pyrimidinyl and isoxazolyl, aminodiphenyl, aminodiphenylether andazobenzenyl are suitable.

Such radicals may be mono- or poly-substituted, for example byC₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, e.g. fluorine, bromineor chlorine, nitro, trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl,phenylsulfonyl, benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or bydi-(hydroxy-C₁-C₄alkyl)-aminosulfonyl.

Examples of suitable radicals Q are as follows:

R is the radical of an unsubstituted or substituted, water-solublealiphatic or aromatic amine. Preferably, R is a radical of formula—NR₁₆R₁₇, wherein R₁₆ is H; unsubstituted linear or branched C₁-C₆alkylor linear or branched C₁-C₆alkyl, which is substituted by one or moreidentical or different substituent selected from the group consisting ofOC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇is unsubstituted linear or branched C₁-C₆alkyl or linear or branchedC₁-C₆alkyl, which is substituted by one or more identical or differentsubstituent selected from the group consisting of OC₁-C₄alkyl, COOH,COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH.

More preferably, R is a radical of —NR₁₆R₁₇, wherein R₁₆ and R₁₇ areC₁-C₄alkyl, mono-substituted by OC₁-C₂alkyl, COOH, COOC₁-C₂alkyl, SO₃H,NH₂, CN, halogen or OH. Example for suitable amine compounds (R—H) aremethylaminoacetic acid (sarcosine), methylaminobutyric acid,methylaminopropionic acid, ethylaminoacetic acid, ethylaminobutyricacid, 1-methylamino-ethane-2-sulfonic acid,1-ethylamino-ethane-2-sulfonic acid and 1-methylamino-propane-3-sulfonicacid.

Preferably, R also signifies the radical of unsubstituted aniline; theradical of unsubstituted aminonaphthalene; the radical of aniline oraminonaphthalene, wherein the phenyl or the naphthyl ring is substitutedby one or more identical or different substituent selected from thegroup consisting of COOH, SO₃H, CN, halogen, SO₂C₁-C₂alkyl,unsubstituted linear or branched C₁-C₄alkyl, linear or branchedC₁-C₄alkyl, substituted by OH, carboxy, COC₁-C₂alkyl orSO₂—N(C₁-C₄alkyl)-(CH₂)₁₋₄SO₃H and wherein the amino radical issubstituted by H, unsubstituted linear or branched C₁-C₄alkyl or linearor branched C₁-C₄alkyl, substituted by OH or carboxy.

Suitable radicals of such aromatic amines are, for example, as follows:

T is an unsubstituted or substituted, water-soluble aliphatic oraromatic residue.

Preferably, T is a linear or branched unsubstituted C₁-C₆alkyl or linearor branched C₁-C₆alkyl, which is substituted by one or more identical ordifferent substituent selected from the group consisting of OC₁-C₄alkyl,COOH, COOC₁-C₂alkyl, SO₃H, NH₂, NH(C₁-C₂alkyl), N(C₁-C₂alkyl)₂, CN,halogen and OH.

More preferably, T is a linear or branched C₁-C₆alkyl, which issubstituted by one or two identical or different substituent selectedfrom the group consisting of COOH, NH₂, NH(C₁-C₂alkyl), N(C₁-C₂alkyl)₂and SO₃H.

Examples for such suitable radicals are —CH₂COOH, —(CH₂)₂COOH,—(CH₂)₃COOH, —CH(NHCH₂CH₃)COOH, —CH₂CH₂SO₃H and —CH₂CH₂CH₂SO₃H.

Preferably, T is also unsubstituted phenyl; unsubstituted naphthyl;phenyl or naphthyl, which are substituted by one or more identical ordifferent substituents selected from the group consisting ofOC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, NH(C₁-C₂alkyl),N(C₁-C₂alkyl)₂, CN, halogen and OH.

Such suitable aromatic residues are, for example, as follows:

A preferred embodiment of the present invention is a method of colouringporous material, which comprises applying to the material beingcoloured, in any desired order successively, or simultaneously,

-   a) at least one capped diazonium compound of formula (1)    and/or at least one compound of formula (2)    and/or at least one compound of formula (3)    wherein-   Q is an unsubstituted phenyl; naphthyl; thiophenyl; 1,3-thiazolyl;    1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl; imidazolyl;    1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl; pyrazolyl;    benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl; pyrimidinyl;    isoxazolyl; aminodiphenyl; aminodiphenylether and azobenzenyl or-   Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl,    1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,    1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,    benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl    and isoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl    which is mono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy,    C₁-C₄alkylthio, halogen, e.g. fluorine, bromine or chlorine, nitro,    trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl, phenylsulfonyl,    benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,    C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or by    di-(hydroxy-C₁-C₄alkyl)-aminosulfonyl,-   R is a radical of formula —NR₁₆R₁₇, wherein R₁₆ is H; unsubstituted    linear or branched C₁-C₆alkyl or linear or branched C₁-C₆alkyl,    which is substituted by one or more identical or different    substituent selected from the group consisting of OC₁-C₄alkyl, COOH,    COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇ is    unsubstituted linear or branched C₁-C₆alkyl or linear or branched    C₁-C₆alkyl, which is substituted by one or more identical or    different substituent selected from the group consisting of    OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, or-   R is the radical of unsubstituted aniline; the radical of    unsubstituted aminonaphthalene; the radical of aniline or    aminonaphthalene, wherein the phenyl or the naphthyl ring is    substituted by one or more identical or different substituent    selected from the group consisting of COOH, SO₃H, CN, halogen,    SO₂C₁-C₂alkyl, unsubstituted linear or branched C₁-C₄alkyl, linear    or branched C₁-C₄alkyl, substituted by OH, carboxy, COC₁-C₂alkyl or    SO₂—N(C₁-C₄alkyl)-(CH₂)₁₋₄SO₃H and wherein the amino radical is    substituted by H, unsubstituted linear or branched C₁-C₄alkyl or    linear or branched C₁-C₄alkyl, substituted by OH or carboxy,-   T is a linear or branched unsubstituted C₁-C₆alkyl or linear or    branched C₁-C₆alkyl, which is substituted by one or more identical    or different substituent selected from the group consisting of OC,    —C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, NH(C₁-C₂alkyl),    N(C₁-C₂alkyl)₂, CN, halogen and OH, or-   T is unsubstituted phenyl; unsubstituted naphthyl; phenyl or    naphthyl, which are substituted by one or more identical or    different substituents selected from the group consisting of    OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, NH(C₁-C₂alkyl),    N(C₁-C₂alkyl)₂, CN, halogen and OH, and-   b) at least one water-soluble coupling component    under conditions such that, initially, coupling does not take place,    and then causing the capped diazonium compound present on the    material to react with the coupling component, with the provisos    that if the water-soluble coupling component is    then the capped diazonium compounds is not    then the capped diazonium compound is not    then the capped diazonium compound is not    then the capped diazonium compound is not    then the capped diazonium compound is not    then the capped diazonium compound is not    then the capped diazonium compound is not    then the capped diazonium compound is not    then the capped diazonium compound is not    then the diazonium capped compound is not

The provisos (i)-(x) exclude the Examples 5-67 of the InternationalApplication PCT/EP02/02146.

A more preferred embodiment of the present invention is a method ofcolouring porous material, which comprises applying to the materialbeing coloured, in any desired order successively, or simultaneously,

-   a) at least one capped diazonium compound of formula (1)    and/or at least one compound of formula (2)    and/or at least one compound of formula (3)    wherein-   Q is an unsubstituted phenyl; naphthyl; thiophenyl; 1,3-thiazolyl;    1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl; imidazolyl;    1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl; pyrazolyl;    benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl; pyrimidinyl;    isoxazolyl; aminodiphenyl; aminodiphenylether and azobenzenyl or-   Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl,    1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,    1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,    benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl    and isoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl    which is mono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy,    C₁-C₄alkylthio, halogen, e.g. fluorine, bromine or chlorine, nitro,    trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl, phenylsulfonyl,    benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,    C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or by    di-(hydroxy-C₁-C₄alkyl)-aminosulfonyl,-   R is a radical of formula —NR₁₆R₁₇, wherein R₁₆ is H; unsubstituted    linear or branched C₁-C₆alkyl or linear or branched C₁-C₆alkyl,    which is substituted by one or more identical or different    substituent selected from the group consisting of OC₁-C₄alkyl, COOH,    COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇ is    unsubstituted linear or branched C₁-C₆alkyl or linear or branched    C₁-C₆alkyl, which is substituted by one or more identical or    different substituent selected from the group consisting of    OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH,-   T is a linear or branched C₁-C₆alkyl, which is substituted by one or    two identical or different substituent selected from the group    consisting of COOH, SO₃H, NH₂, NH(C₁-C₂alkyl) and N(C₁-C₂alkyl)₂, or-   T is unsubstituted phenyl; unsubstituted naphthyl; phenyl or    naphthyl, which are substituted by one or more identical or    different substituents selected from the group consisting of    OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, NH(C₁-C₂alkyl),    N(C₁-C₂alkyl)₂, CN, halogen and OH, and-   b) at least one water-soluble coupling component    under conditions such that, initially, coupling does not take place,    and then causing the capped diazonium compound present on the    material to react with the coupling component, with the same    provisos (i)-(x) as defined above.

An especially preferred embodiment of the present invention is a methodof colouring porous material, which comprises applying to the materialbeing coloured, in any desired order successively, or simultaneously,

-   a) at least one capped diazonium compound of formula (1)    wherein-   Q is an unsubstituted phenyl; naphthyl; thiophenyl; 1,3-thiazolyl;    1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl; imidazolyl;    1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl; pyrazolyl;    benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl; pyrimidinyl;    isoxazolyl; aminodiphenyl; aminodiphenylether and azobenzenyl or-   Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl,    1,3-benzothiazolyl, 2,3-benzothiazolyl, Imidazolyl,    1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,    benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl    and isoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl    which is mono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy,    C₁-C₄alkylthio, halogen, e.g. fluorine, bromine or chlorine, nitro,    trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl, phenylsulfonyl,    benzylsulfonyl, di-C₁C₄alkylaminosulfonyl, C₁-C₄alkyl-carbonylamino,    C₁-C₄alkoxysulfonyl or by di-(hydroxy-C₁-C₄alkyl)-aminosulfonyl,-   R is a radical of formula —NR₁₆R₁₇, wherein R₁₆ is H; unsubstituted    linear or branched C₁-C₆alkyl or linear or branched C₁-C₆alkyl,    which is substituted by one or more identical or different    substituent selected from the group consisting of OC₁-C₄alkyl, COOH,    COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇ is    unsubstituted linear or branched C₁-C₆alkyl or linear or branched    C₁-C₆alkyl, which is substituted by one or more identical or    different substituent selected from the group consisting of    OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and-   b) at least one water-soluble coupling component    under conditions such that, initially, coupling does not take place,    and then causing the capped diazonium compound present on the    material to react with the coupling component, with the same    provisos (i)-(x) as defined above.

A further especially preferred embodiment of the present invention is amethod of colouring porous material, which comprises applying to thematerial being coloured, in any desired order successively, orsimultaneously,

-   a) at least one capped diazonium compound of formula (1)    wherein-   Q is an unsubstituted phenyl; naphthyl; thiophenyl; 1,3-thiazolyl;    1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl; imidazolyl;    1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl; pyrazolyl;    benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl; pyrimidinyl;    isoxazolyl; aminodiphenyl; aminodiphenylether and azobenzenyl or-   Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl,    1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,    1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,    benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl    and isoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl    which is mono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy,    C₁-C₄alkylthio, halogen, e.g. fluorine, bromine or chlorine, nitro,    trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl, phenylsulfonyl,    benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,    C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or by    di-(hydroxy-C₁-C₄alkyl)-aminosulfonyl,-   R is a radical of formula —NR₁₆R₁₇, wherein R₁₆ is H; unsubstituted    linear or branched C₁-C₆alkyl or linear or branched C₁-C₆alkyl,    which is substituted by one or more identical or different    substituent selected from the group consisting of OC₁-C₄alkyl, COOH,    COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇ is    unsubstituted linear or branched C₁-C₆alkyl or linear or branched    C₁-C₆alkyl, which is substituted by one or more identical or    different substituent selected from the group consisting of    OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and-   b) at least one water-soluble coupling component    under conditions such that, initially, coupling does not take place,    and then causing the capped diazonium compound present on the    material to react with the coupling component, with the provisos    that if the capped diazonium compound is    then the water-soluble coupling component is not    wherein R₁₈ signifies H, CH₃, F, NO₂, OCH₃ then water-soluble    coupling component is not    wherein    -   R₁₉ signifies OCH₃, CH₃ and    -   R₂₀ signifies Cl, CH₃, NO₂, NHCOCH₃        then water-soluble coupling component is not        wherein    -   R₂₁ signifies Cl, CH₃, SO₃′, OCH₃    -   R₂₂ signifies CH₃, Cl, OCH₃        then the water-soluble coupling component is not        then the water-soluble coupling component is not        then the water-soluble coupling component is not        then the water-soluble coupling component is not

A further embodiment of the present invention is a method of colouringporous material, which comprises applying to the material beingcoloured, in any desired order successively, or simultaneously,

-   a) at least two capped diazonium compounds as defined above and-   b) at least one water-soluble coupling component    under conditions such that, initially, coupling does not take place,    and then causing the capped diazonium compound present on the    material to react with the coupling component.

A further embodiment of the present invention is a method of colouringporous material, which comprises applying to the material beingcoloured, in any desired order successively, or simultaneously,

-   a) at least one capped diazonium compound as defined above and-   b) at least two water-soluble coupling components    under conditions such that, initially, coupling does not take place,    and then causing the capped diazonium compound present on the    material to react with the coupling component.

A further embodiment of the present invention is a method of colouringporous material, which comprises applying to the material beingcoloured, in any desired order successively, or simultaneously,

-   a) at least two capped diazonium compounds as defined above and-   b) at least two water-soluble coupling components    under conditions such that, initially, coupling does not take place,    and then causing the capped diazonium compound present on the    material to react with the coupling component.

Suitable coupling components are, for example, the usual couplingcomponents customarily used for azo dyes and known from the pertinentliterature, e.g. coupling components from the benzene series,naphthalene series, open-chain methylene-active compounds (e.g.acylacetarylamides) and the heterocyclic series.

They are, for example, acylacetarylamides, phenols, naphthols,pyridones, quinolones, pyrazoles, indoles, diphenylamines, anilines,aminopyridines, pyrimidones, naphthylamines, aminothiazoles, thiophenesor hydroxypyridines.

Acetoacetanilides, phenols, anilines, diphenylamines, naphthylamines,indoles, quinolines, pyridones, pyrazoles and aminopyridines areespecially suitable.

Such coupling components may carry further substituents, for exampleamino, alkylamino, dialkylamino, halogen, alkyl, alkoxy, aryl,especially phenyl or naphthyl, or aryloxy, but especially a groupimparting water solubility, e.g. hydroxy, carboxy or sulfo.

The coupling components preferably carry one or two such groupsimparting water solubility. Examples of suitable coupling components areas follows:

A further embodiment of the present invention is a method of colouringporous material, which comprises applying to the material beingcoloured, in any desired order successively, or simultaneously,

-   a) at least one capped diazonium compound of formula (1)    and/or at least one compound of formula (2)    and/or at least one compound of formula (3)    wherein-   Q is an unsubstituted phenyl; naphthyl; thiophenyl; 1,3-thiazolyl;    1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl; imidazolyl;    1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl; pyrazolyl;    benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl; pyrimidinyl;    isoxazolyl; aminodiphenyl; aminodiphenylether and azobenzenyl or-   Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl,    1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,    1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,    benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl    and isoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl    which is mono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy,    C₁-C₄alkylthio, halogen, e.g. fluorine, bromine or chlorine, nitro,    trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl, phenylsulfonyl,    benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,    C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or by    di-(hydroxy-C₁-C₄alkyl)-aminosulfonyl,-   R is a radical of formula —NR₁₆R₁₇, wherein R₁₅ is H; unsubstituted    linear or branched C₁-C₆alkyl or linear or branched C₁-C₆alkyl,    which is substituted by one or more identical or different    substituent selected from the group consisting of OC₁-C₄alkyl, COOH,    COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇ is    unsubstituted linear or branched C₁-C₆alkyl or linear or branched    C₁-C₆alkyl, which is substituted by one or more identical or    different substituent selected from the group consisting of    OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH,-   T is a linear or branched C₁-C₆alkyl, which is substituted by one or    two identical or different substituent selected from the group    consisting of COOH, SO₃H, NH₂, NH(C₁-C₂alkyl) and N(C₁-C₂alkyl)₂, or-   T is unsubstituted phenyl; unsubstituted naphthyl; phenyl or    naphthyl, which are substituted by one or more identical or    different substituents selected from the group consisting of    OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, NH(C₁-C₂alkyl),    N(C₁-C₂alkyl)₂, CN, halogen and OH, and-   b) at least one water-soluble coupling component selected from the    group consisting of acylacetarylamides, phenols, naphthols,    pyridones, quinolones, pyrazoles, indoles, diphenylamines, anilines,    aminopyridines, pyrimidones, naphthylamines, aminothiazoles,    thiophenes or hydroxypyridines, which all may carry further    substituents, for example amino, alkylamino, dialkylamino, halogen,    alkyl, alkoxy, aryl, especially phenyl or naphthyl, or aryloxy, but    especially a group imparting water solubility, e.g. hydroxy, carboxy    or sulfo, under conditions such that, initially, coupling does not    take place, and then causing the capped diazonium compound present    on the material to react with the coupling component, with the same    provisos (i)-(x) as defined above.

An especially preferred embodiment of the present invention is a methodof colouring porous material, which comprises applying to the materialbeing coloured, in any desired order successively, or simultaneously,

-   a) at least one capped diazonium compound of formula (1)    wherein-   Q is an unsubstituted phenyl; naphthyl; thiophenyl; 1,3-thiazolyl;    1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl; imidazolyl;    1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl; pyrazolyl;    benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl; pyrimidinyl;    isoxazolyl; aminodiphenyl; aminodiphenylether and azobenzenyl or-   Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl,    1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,    1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,    benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl    and isoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl    which is mono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy,    C₁-C₄alkylthio, halogen, e.g. fluorine, bromine or chlorine, nitro,    trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl, phenylsulfonyl,    benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,    C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or by    di-(hydroxy-C₁-C₄alkyl)-aminosulfonyl,-   R is a radical of formula —NR₁₆R₁₇, wherein R₁₆ is H; unsubstituted    linear or branched C₁-C₆alkyl or linear or branched C₁-C₆alkyl,    which is substituted by one or more identical or different    substituent selected from the group consisting of OC₁-C₄alkyl, COOH,    COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇ is    unsubstituted linear or branched C₁-C₆alkyl or linear or branched    C₁-C₆alkyl, which is substituted by one or more identical or    different substituent selected from the group consisting of    OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and-   b) at least one water-soluble coupling component selected from the    group consisting of    under conditions such that, initially, coupling does not take place,    and then causing the capped diazonium compound present on the    material to react with the coupling component, with the same    provisos (i)-(x) as defined above.

An especially preferred embodiment of the present invention is a methodof colouring porous material, which comprises applying to the materialbeing coloured, in any desired order successively, or simultaneously,

-   a) at least one capped diazonium compound of formula (1)    wherein-   Q is an unsubstituted phenyl; naphthyl; thiophenyl; 1,3-thiazolyl;    1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl; imidazolyl;    1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl; pyrazolyl;    benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl; pyrimidinyl;    isoxazolyl; aminodiphenyl; aminodiphenylether and azobenzenyl or-   Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl,    1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,    1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,    benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl    and isoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl    which is mono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy,    C₁-C₄alkylthio, halogen, e.g. fluorine, bromine or chlorine, nitro,    trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl, phenylsulfonyl,    benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,    C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or by    di-(hydroxy-C₁-C₄alkyl)-aminosulfonyl,-   R is a radical of formula —NR₁₆R₁₇, wherein R₁₆ is H; unsubstituted    linear or branched C₁-C₆alkyl or linear or branched C₁-C₆alkyl,    which is substituted by one or more identical or different    substituent selected from the group consisting of OC₁-C₄alkyl, COOH,    COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇ is    unsubstituted linear or branched C₁-C₆alkyl or linear or branched    C₁-C₆alkyl, which is substituted by one or more identical or    different substituent selected from the group consisting of    OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and-   b) at least one water-soluble coupling component selected from the    group consisting of    under conditions such that, initially, coupling does not take place,    and then causing the capped diazonium compound present on the    material to react with the coupling component, with the same    provisos (i_(a))-(vii_(a)) as defined above.

An important embodiment of the present invention is a method ofcolouring porous material, which comprises applying to the materialbeing coloured, in any desired order successively, or simultaneously,

-   a) at least one capped diazonium compound of formula (1)    and/or at least one compound of formula (2)    and/or at least one compound of formula (3)    wherein-   Q is-   b) at least one water-soluble coupling component selected from the    group consisting of    under conditions such that, initially, coupling does not take place,    and then causing the capped diazonium compound present on the    material to react with the coupling component, with the same    provisos (i)-(x) as defined above.

The amines of formulae Q-NH₂ and R—H and the coupling components areknown or can be synthesised in a manner known per se.

The compounds of formulae (2) and (3) are also known or can besynthesised in a manner known per se.

The compounds of formula (1) wherein R is the radical of an aliphaticamine are likewise known or can be synthesised in a manner known per se.The compounds of formula

wherein

-   Q is an unsubstituted or substituted phenyl, naphthyl, thiophenyl,    1,3-thiazolyl, 1,2-thiazolyl, 1,3-benzothiazolyl,    2,3-benzothiazolyl, imidazolyl, 1,3,4-thiadiazolyl,    1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl, benzimidazolyl,    benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl and isoxazolyl,    aminodiphenyl, aminodiphenylether or azobenzenyl or-   Q is phenyl, naphthyl, thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl,    1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,    1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,    benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl    and isoxazolyl, aminodiphenyl, aminodiphenylether or azobenzenyl    mono- or polysubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio,    halogen, e.g. fluorine, bromine or chlorine, nitro, trifluoromethyl,    CN, SCN, C₁-C₄alkylsulfonyl, phenylsulfonyl, benzylsulfonyl,    di-C₁-C₄alkylaminosulfonyl, C₁-C₄alkylcarbonylamino,    C₁-C₄alkoxysulfonyl or by di-(hydroxy-C₁-C₄alkyl)-aminosulfonyl, and-   R′ is a the radical of unsubstituted aniline; the radical of    unsubstituted aminonaphthalene; the radical of aniline or    aminonaphthalene, wherein the phenyl or the naphthyl ring is    substituted by one or more identical or different substituent    selected from the group consisting of COOH, SO₃H, CN, halogen,    SO₂C₁-C₂alkyl, unsubstituted linear or branched C₁-C₄alkyl, linear    or branched C₁-C₄alkyl, substituted by OH, carboxy, COC₁-C₂alkyl or    SO₂—N(C₁-C₄alkyl)-(CH₂)₁₋₄SO₃H and wherein the amino radical is    substituted by H, unsubstituted linear or branched C₁-C₄alkyl or    linear or branched C₁-C₄alkyl, substituted by OH or carboxy, are    novel,    with the exception of the compound of formula

The compounds of formula (4) can likewise be prepared in a manner knownper se; for example, an amine of formula q-NH₂ is, in customary manner,diazotised and coupled to an amine of formula R′—H, there coming intoconsideration as amines R—H only those compounds that couple at thenitrogen atom rather than at a carbon atom of the aromatic ring. Suchcompounds are, preferably, aniline derivatives substituted in the4-position.

The multiplicity of shades of the dye, which results by the methodaccording to the present invention, can be increased by combination withother dyes. The present invention relates also to the colouration ofhair with a dye, which results by the method according to the presentinvention, and at least one other dye.

The dye, which results by the combination of at least one cappeddiazonium compound and at least one coupling compound, can be combinedwith dyes of the same or different class of dyes, especially with directdyes, oxidation dyes; dye precursor combinations of a coupler compoundand a diazotized compound, or a capped diazotized compound; and/orcationic reactive dyes.

Direct dyes are natural or synthetic, they are uncharged, cationic oranionic, such as acid dyes.

Oxidation dye denotes also for oxidation dye precursors, which are fromthe group of the developer and coupler compounds.

In the context of the invention the single classes of dyes comprise thedyes defined in the Color Index of the Society of Textile Chemist andColorist.

In the following suitable direct dyes for the combination with themethod according to the present invention are described.

Directs dyes are for example described in “Dermatology”, edited by Ch.Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986,Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, pages 248-250,and in “Europäisches Inventar der Kosmetikrohstoffe”, 1996, published byThe European Commission, obtainable in diskette form from theBundesverband der deutschen Industrieund Handelsunternehmen fürArzneimittel, Reformwaren und Körperpflegemittel e.V., Mannheim.

Preferred direct dyes, which are suitable as single dye or incombination with other direct dyes, especially for semi permanentdyeing, are:

-   2-Amino-3-nitrophenol, 2-Amino-4-hydroxyethylamino-anisole sulfate,    2-Amino-6-chloro-4-nitrophenol,    2-Chloro-5-nitro-N-hydroxyethylene-p-phenylendiamine,    2-Hydroxyethyl-picramic acid,    2,6-Diamino-3-((pyridine-3yl)-azo)pyridine,    2-Nitro-5-glyceryl-methylaniline,    3-Methylamino-4-nitro-phenoxyethanol,    4-Amino-2-nitrodiphenyleneamine-2′-carboxilic acid,    6-Nitro-1,2,3,4,-tetrahydroquinoxaline,    4-N-Ethyl-1,4-bis(2′-hydroxyethylamino-2-nitrobenzene hydrochloride,    1-Methyl-3-nitro-4-(2′-hydroxyethyl)-aminobenzene,    3-Nitro-p-hydroxyethyl-aminophenol, 4-Amino-3-nitrophenol,    4-Hydroxypropylamine-3-nitrophenol (BN),    Hydroxy-anthrylaminopropylmethyl morphlino methosulfat,    4-Nitrophenyl-aminoethylurea, 6-Nitro-p-toluidine, Acid Blue 62,    Acid Blue 9, Acid Red 35, Acid Red 87 (Eosin), Acid Violet 43, Acid    Yellow 1, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9,    Basic Blue 12, Basic Blue 26, Basic Blue 99, Basic Brown 16, Basic    Brown 17, Basic Red 2, Basic Red 22, Basic Red 76, Basic Violet 14,    Basic Yellow 57, Basic Yellow 9, Disperse Blue 3, Disperse Orange 3,    Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse    Black 9, Fast Green FCF, HC-Blue 2, HC-Blue 7, HC-Blue 8, HC-Blue    12, HC-Orange 1, HC-Orange 2, HC-Red 1, HC-Red 10-11, HC-Red 13,    HC-Red 16, HC-Red 3, HC-Red BN, HC-Red 7, HC-Violet 1, HC-Violet 2,    HC-Yellow 2, HC-Yellow 5, HC-Yellow 5, HC-Yellow 6, HC-Yellow 7,    HC-Yellow 9, HC-Yellow 12, HC-Red 8,    Hydroxyethyl-2-nitro-p-toluidine,    N,N-Bis-(2-Hydroxyethyl)-2-nitro-p-phenylendiamine (BS), Picramic    Acid, Solvent Green 7.

Preferred direct dyes, which are suitable as single dye or incombination with other direct dyes or oxidative dyes and oxidizationagents, especially for semi permanent dyeing and permanent dyeing, are:

-   Disperse Violet 4, Picramic acid,    N,N′-Bis-(2-Hydroxyethyl)-2-nitro-p-phenylendiamine, HC Yellow No.    5, HC Blue No. 2, HC Yellow No.    2,2-Chloro-5-nitro-N-hydroxyethyl-p-phenylendiamine, HC Red No.    3,4-Amino-3-nitrophenol, Basic Blue 99, 2-Hydroxyethyl Picramic    acid, HC Yellow No. 6, Hydroxyethyl-2-nitro-p-toluidine,    2-Amino-6-chloro-4-nitrophenol, 4-Hydroxypropylamino-3-nitrophenol,    Basic Red 2, HC Red No. 16 and HC Blue No. 16.

In the following suitable cationic dyes for the combination with themethod according to the present invention are described.

Preferred cationic dyes are described

-   -   in WO 95/01772, especially on page 2, line 7 to page 4, line 1,        and especially on page 4, line 35 to page 8, line 21 and on        pages 11 to 27, or    -   in WO 01/66646, especially on page 1, line 18 to page 3, line        16, and preferred from page 16, line 20 to page 22, and cationic        dyes as described on pages 10 to 17, or    -   in EP 970 685, especially on page 2, line 44 to page 9, line 56        and preferably on page 9, line 58 to page 48, line 12, or    -   direct dyes as described in DE-A-19 713 698, especially page 2,        line 61 to page 3, line 43, or    -   direct dyes and oxidizing agent as described in WO 97/20545,        especially on page 1, lines 4 to 10, in particular on page 3,        lines 24 to 32, and on page 11, line 6 to page 13, line 19,        especially with direct dyes as described on page 5, line 28 to        page 8, line 20, or    -   cationic dyes and anionic UV-absorbers as described in EP 1 166        752, especially on page 3, line 20 to page 4, line 21, in        particular with UV absorber on page 4, lines 26 to 3, and        especially on page 7, line 47 to page 9, line 56.

More preferred are cationic dyes as described in WO 01/66646, especiallyon page 16, example 1, and on page 19, example 4, or as described in WO95/01772, especially on page 11, example 1, and on page 13, example 4,or as described in WO 01/11708, especially example 6, compound offormula 106.

Also very suitable for combination with the method according to theinvention are cationic nitroaniline and anthraquinone dyes, for examplethose described in the following patent specifications: U.S. Pat. No.5,298,029, especially in column 2, line 33 to column 5, line 38; U.S.Pat. No. 5,360,930, especially in column 2, line 38 to column 5, line49; U.S. Pat. No. 5,169,403, especially in column 2, line 30 to column5, line 38; U.S. Pat. No. 5,256,823, especially in column 4, line 23 tocolumn 5, line 15; U.S. Pat. No. 5,135,543, especially in column 4, line24 to column 5, line 16; EP-A-818 193, especially on page 2, line 40 topage 3, line 26; U.S. Pat. No. 5,486,629, especially in column 2, line34 to column 5, line 29; and EP-A-758 547, especially on page 7, line 48to page 8, line 19.

Also very suitable for combination with the method according to theinvention are mixtures of cationic dyes with other dyes:

-   -   mixtures of at least two cationic dyes as described in WO        95/01772, especially on page 8, line 34 to page 10, line 22 with        the given preferences, or    -   combinations of Pyrazolo-[1,5-a]-pyrimidines with at least one        cationic dye as described in EP 998,908, especially on page 2,        line 34 to line 42, with preferred Pyrazolo-[1,5-a]-pyrimidines        as described in EP 998,908, especially on page 2, line 48 to        page 4, line 3, and with preferred cationic direct dyes as        described in EP 998,908, especially on page 4, line 22 to page        47, line 24, or    -   combinations of cationic dyes as described in FR-2788432,        especially on page 53, line 1 to page 63, line 23, especially a        combination of cationic dyes with Arianors in FR-2788432,        especially on pages 51 to 52, or especially a combination with        at least one Basic Brown 17, Basic brown 16, Basic Red 76 and        Basic Red 118, and/or at least one Basic Yellow 57, and/or at        least one Basic Blue 99, or    -   combinations of direct dyes and/or an oxidation dye and        oxidizing agents in the form of permanent-wave fixing solution,        especially with direct dyes as described in DE-A-19 713 698,        especially page 4, line 65 to page 35, line 59, or    -   combinations of cationic dyes and an oxidation dye of the        developer compound type and oxidizing agents as described in EP        850 638, especially on page 2, line 27 to page 7, line 46 and        preferred on page 7, line 20 to page 9, line 26, or    -   combinations of an extemporaneous mixture of a composition (A)        containing one or more oxidation dye precursors and optionally        one or more couplers, and of a composition (B), in powder form,        containing one or more direct dye, preferably cationic,        optionally dispersed in an organic pulverulent excipient and/or        a mineral pulverulent excipient, and a composition (C)        containing one or more oxidizing agent as described in U.S. Pat.        No. 6,190,421, especially in column 2, lines 2 to 1, and        preferably with oxidation dye precursors as described in column        2, line 35 to column 5, line 13, and preferably with direct dyes        as described in column 5, line 30 to column 7, line 14, or    -   a ready-to-use composition comprising, at least one oxidation        base, at least one cationic direct dye and at least one enzyme        of 2-electron oxidoreductase type in the presence of at least        one donor for the said enzyme as described in U.S. Pat. No.        6,228,129, especially in column 26, line 26 to column 27, line 9        with cationic direct dyes as described in column 8, line 17 to        column 13, line 65, especially those as described in column 20,        line 11 to line 19, in column 23, line 61 to column 24, line 25,        or    -   compositions of at least one direct cationic dye and at least        one nitrated benzene dye as described in WO 99/20235 on page 2,        line 1 to page 7, line 9, and on page 39, line 1 to page 40b        line 11, with cationic direct dyes as described on page 8, line        12 to page 25 line 6, and nitro benzene direct dyes as described        on page 26, line 7 to page 30, line 15, or    -   compositions of at least one direct cationic dye and at least        one autooxidisable oxidation dye, especially benzene, indol and        indoline derivatives as described in WO 99/20234, with in        preferred direct dyes as given on page 2, line 17 to page 26,        line 4, and autooxidisable oxidation dye as described especially        on page 26, line 10 to page 28, line 15, or    -   oxidation dyeing compositions of at least one direct dye and at        least one meta-Aminophenol derivative and at least one developer        compound and an oxidizing agent as described in EP 850 636,        especially on page 5, line 41 to page 7, line 52, and preferably        on page 19, line 50 to page 22, line 12, with preferred direct        dye as described on page 18, lines 1 and 2 in connection with        page 7, line 53 to page 17, line 55, and with preferred        meta-Aminophenol derivatives as described on page 7, line 47 to        line 52, and with preferred developer compounds as described on        page 6, line 10 to page 7, line 46, or    -   oxidation dyeing compositions of at least one direct dye and at        least one developer compound selected from the group of        para-Phenylenediamine derivatives and Bis-Phenylalkylenediamine        and, and at least one coupler compound selected from the group        of meta-Diphenols and an oxidizing agent, as described in        EP-A-850 637, especially on page 6, line 50 to page 8, line 44,    -   oxidation dyeing compositions with cationic couplers, as        described in WO 99/48856, especially on page 9, line 16 to page        13, line 8, and page 11, line 20 to page 12, line 13, or    -   cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives,        as described in EP 998 908, especially on page 2, line 34 to        page 4, line 23, or    -   arianoren and/or oxidative dyes, as described in FR-2 788 432,        especially on page 2, line 16 to page 3, line 16, and page 5,        line 19 to page 14, line 8, and combinations with cationic dyes        as described on page 14, line 23 and following, or    -   oxidative dye precursors (unsaturated aldehyde and coupler        compounds), as described in German Patent Application 197 172        24, especially unsaturated aldehydes as described on page 2,        line 50 to line 66 and page 3 line 8 to line 12 are used as        developer compounds, and primary and secondary amino group        compounds, nitrogen-containing heterocyclic compounds, amino        acids, oligopeptids, aromatic hydroxy compounds, CH-active        compounds as described on page 3, line 42 to page 5 line 25 are        used as coupler compounds.

Also cationic azo dyes, e.g. according to GB-A-2 319 776, as well as theoxazine dyes described in DE-A-29 912 327 and mixtures thereof with theother direct dyes mentioned therein, can likewise readily be combined.

Especially preferred direct dye mixtures comprising a dye of formula (1)of WO 01/66646, and also the yellow dye according to Example 1 of WO95/1772 and/or the red dye according to Example 4 of WO 95/1772 and/orthe orange dye according to Example 46 of WO 95/1772.

No particular limitation is imposed on the acid dye used in the presentinvention so far as it is a water-soluble acid dye.

For the purpose of further modification of color shades, the method ofcolouring according to the invention may comprise customary acid dyes,for example from the group of the compounds known by the internationalnames (Color index), or trade names.

Preferred examples of acid dyes are described in U.S. Pat. No.6,248,314, they include Red Color No. 120, Yellow Color No. 4, YellowColor No. 5, Red Color No. 201, Red Color No. 227, Orange Color No. 205,Brown Color No. 201, Red Color No. 502, Red Color No. 503, Red Color No.504, Red Color No. 506, Orange Color No. 402, Yellow Color No. 402,Yellow Color No. 406, Yellow Color No. 407, Red Color No. 213, Red ColorNo. 214, Red Color No. 3, Red Color No. 104, Red Color No. 105(1), RedColor No. 106, Green Color No. 2, Green Color No. 3, Orange Color No.207, Yellow Color No. 202(1), Yellow Color No. 202(2), Blue Color No.202, Blue Color No. 203, Blue Color No. 205, Blue Color No. 2, YellowColor No. 203, Blue Color No. 201, Green Color No. 201, Blue Color NO.1, Red Color No. 230(1), Red Color No. 231, Red Color No. 232, GreenColor No. 204, Green Color No. 205, Red Color No. 401, Yellow Color No.403(1), Green Color No. 401, Green Color No. 402, Black Color No. 401and Purple Color No. 401, especially Black Color No. 401, Purple Color401, Orange Color No. 205.

These acid dyes may be used either single or in any combination thereof.

Preferably they are incorporated in a proportion of 0.001-5% by weight(hereinafter indicated merely by “%”), particularly 0.005-4%, moreparticularly 0.2-3% based on the total weight of the composition, fromthe viewpoint of practical use in that a sufficient hair-dyeing effectis achieved, and the hand skin is scarcely smeared.

Also very suitable for combination with the method according to theinvention are uncharged dyes, for example from the group of thenitroanilines, nitrophenylenediamines, nitroaminophenols,anthraquinones, indophenols, phenazines, phenothiazines, bispyrazolonsor bispyrazol aza derivatives or methines.

Also very suitable for combination with the method according to theinvention are oxidation dyes.

Suitable oxidation dyes are described for example in

-   -   German Patent Application 19 94 450, especially on page 6, line        6 to line 64, or    -   German Patent Application 19 959 479, especially in column 2,        line 6 to column 3, line 11, or    -   in the series “Dermatology”, edited by Ch. Culnan, H. Maibach,        Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch.        Zviak, The Science of Hair Care, chapter 8, on pages 264-267        (oxidation dyes), or    -   in German Patent Application 19 717 224; unsaturated aldehydes        as described on page 2, line 50 to line 66 and on page 3 line 8        to line 12 are used as developer compounds, and primary and        secondary amino group compounds, nitrogen-containing        heterocyclic compounds, amino acids, oligopeptids, aromatic        hydroxy compounds, CH-active compounds as described on page 3,        line 42 to page 5 line 8 are used as coupler compounds.

Oxidation dye precursors of the developer type are for example primaryaromatic amines, which are substituted in the para- or ortho-positionwith a substituted or unsubstituted hydroxy- or amino residue, ordiaminopyridine derivatives, heterocyclic hydrazones, 4-amino-pyrazolderivatives, 2,4,5,6-tetraminopyrimidin derivatives, or unsaturatedaldehydes as described in German Patent Application 19 717 224,especially on page 2, line 50 to line 66 and on page 3 line 8 to line12, or cationic developer compounds as described in WO 00/43367,especially on page, 2 line 27 to page 8, line 24, in particular on page9, line 22 to page 11, line 6.

Also very suitable for combination with the method according to theinvention are developer dyes in their physiological compatible acidaddition salt form, such as hydrochloride or sulfate. Developer dyeswhich have aromatic OH substituents are also suitable in their salt formwith base, such as alkalimetalphenolates.

Preferred developer compounds are:

-   1,4-diamino-benzene (p-phenylendiamine),    1,4-diamino-2-methyl-benzene (p-toluylen-diamine),    1,4-diamino-2,6-dimethyl-benzene, 1,4-diamino-2,5-dimethyl-benzene,    1,4-diamino-2,3-dimethyl-benzene, 2-chloro-1,4-diaminobenzene,    4-phenylamino-aniline, 4-di-methylamino-aniline,    4-diethylamino-aniline, hydroxyethyl-p-phenylendiamine,    1-(2′-hydroxy-ethyl)-2,5-diaminobenzene,    N,N-bis-(2-hydroxyethyl)-p-phenylendiamine,    4-[(2-methoxyethyl-)amino]-aniline,    4-[(3-hydroxypropyl)amino]-aniline,    hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine) hydrochloride,    1,4-diamino-2-(2-hydroxyethyl)-benzene,    1,4-diamino-2-(1-methylethyl)-benzene,    2-(2,5-diaminophenoxy)-ethanol,    1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol,    bis-(2-hydroxy-5-aminophenyl)-methane,    1,4-bis-(4-aminophenyl)-diazacycloheptane,    1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctan,    1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane,    hydroxyethyl-3,4-methylenedioxyaniline, p-aminophenol,    o-aminophenol, m-aminophenol, 2-amino-6-methyl-phenol,    4-methylaminophenol sulfate, 4-amino-m-cresol, 6-amino-m-cresol,    6-amino-m-cresol, 2-amino-4-hydroxyethylaminoanisole,    2-amino-5-methyl-phenol, 4-amino-3-methylphenol,    4-methylamino-phenol, 2-aminomethyl-4-aminophenol,    4-amino-2-[(2-hydroxyethyl)-amino]methyl-phenol,    4-amino-2-(2-hydroxyethoxy)-phenol,    4-amino-2-(methoxymethyl)-phenol, 4-amino-2-(2-hydroxyethyl)-phenol,    2-hydroxymethylamino-4-aminophenol, bis-(4-aminophenyl)amine,    4-amino-3-fluorphenol, 2-hydroxymethyl-4-aminophenol,    4-amino-2-(diethylamino)-methyl)-phenol, 5-amino-salicylsäure,    2,5-diamino-pyridine, 2-amino-3-hydroxy-pyridine,    2,6-dimethoxy-3,5-diamino-pyridine, 2,4,5,6-tetraminopyrimidine,    2-hydroxy-4,5,6-triaminopyrimidine,    4-hydroxy-2,5,6-triaminopyrimidine,    2,4-dihydroxy-5,6-diaminopyrimidine,    2-dimethylamino-4,5,6-triaminopyrimidine,    2,5,6-triamino-4-(1H)-pyrimidone, further 4,5-diaminopyrazol    derivatives as described in EP 0 740 741 or WO 94/08970, especially    4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazol,    4,5-diamino-1-(1-methylethyl)-1H-pyrazol,    4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazol,    1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazol,    4,5-diamino-1-methyl-1H-pyrazol.

More preferred developer dyes are p-phenylendiamine, p-toluylendiamine,p-aminophenol, m-aminophenol, o-aminophenol,N,N-bis-(2-hydroxyethyl)-p-phenylendiamine sulfate,2-amino-4-hydroxyethylaminoanisole sulfate,hydroxyethyl-3,4-methylenedioxyaniline,1-(2′-hydroxyethyl)-2,5-diaminobenzene,2,6-dimethoxy-3,5-diamino-pyridine,hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine) hydrochloride,hydroxyethyl-p-phenylendiamine sulfate, 4-amino-3-methylphenol,4-methylaminophenol sulfate, 2-aminomethyl-4-aminophenol,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazol, 4-amino-m-cresol,6-amino-m-cresol, 5-amino-6-chloro-cresol, 2,4,5,6-tetraminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidinesulfate.

Preferred oxidation dye precursors of the coupler type are for examplem-phenylendiamine derivatives, naphthole, resorcine and resorcinederivatives, pyrazolone and m-aminophenol derivatives.

Especially preferred coupler compounds areN-(3-dimethylamino-phenyl)-urea, 4-amino-2-hydroxytoluene,2-methyl-5-hydroxyethylaminophenol, 2,4-diaminophenoxyethanol,2-amino-4-[(2-hydroxyethyl)amino]-anisole, p-aminophenol, m-aminophenoland its derivatives, especially 5-amino-2-methylphenol,5-(3-hydroxypropylamino)-2-methylphenol,3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol,2,6-dimethyl-3-aminophenol,3-trifluoroacetylamino-2-chloro-6-methylphenol,5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,5-(2′-hydroxyethyl)-amino-2-methylphenol, 3-(diethylamino)-phenol,N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-(methylamino)-benzene,3-(ethyl-amino)-4-methylphenol and 2,4-dichloro-3-aminophenol,

-   o-aminophenol and its derivatives, such as    5-methyl-2-(1-methylamino)-phenol, 3-di -methylamino-phenol,    3-diethylamino-phenol, 5-amino-2-methyl-phenol,    5-amino-4-fluor-2-methyl-phenol, 5-amino-4-methoxy-2-methyl-phenol,    5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichlor-phenol,    5-amino-2,4-dichlor-phenol, 3-amino-2-methyl-phenol,    3-amino-2-chlor-6-methyl-phenol, 3-amino-phenol,    2-[(3-hydroxy-phenyl)amino]-acetamide,    5-[(2-hydroxyethyl)amino]-2-methyl-phenol,    3-[(2-hydroxy-ethyl)amino]-phenol, 3-[(2-methoxyethyl)amino]-phenol,    5-amino-2-ethyl-phenol, 2-(4-amino-2-hydroxyphenoxy)-ethanol,    5-[(3-hydroxypropyl)amino]-2-methyl-phenol,    3-[(2,3-dihydroxypropyl)amino]-2-methyl-phenol,    3-[(2-hydroxyethyl)amino]-2-methyl-phenol,-   m-diaminobenzene and its derivatives such as    2,4-diaminophenoxyethanol, 1,3-bis-(2,4-diaminophenoxy)-propane,    1-methoxy-2-amino-4-(2′-hydroxyethylamino)-benzene,    1,3-bis-(2,4-diaminophenyl)-propane,    3-[(2-aminoethyl)amino]-aniline, 1,3-di(2,4-diaminophenoxy)-propane,    1,3-diamino-2,4-dimethoxy-benzene,    2,6-bis(2-hydroxyethyl)amino-toluene,    di(2,4-diaminophenoxy)-methane,    3-[di(2-hydroxyethyl-)amino]-aniline,    2,6-bis-(2-hydroxyethylamino)-1-methylbenzene and    1-amino-3-bis-(2′-hydroxyethyl)-aminobenzene,-   o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid    and 2,3-diamino-1-methylbenzene,    2,4-diamino-1-fluor-5-methyl-benzene,    2,4-diamino-1-methoxy-5-methyl-benzene,    1-(2-aminoethoxy)-2,4-diaminobenzene,    2-amino-1-(2-hydroxyethoxy)-4-methylamino-benzene,    2,4-diaminophenoxy-acetic acid,    2,4-di-amino-1-ethoxy-5-methyl-benzene,    3-[(2-hydroxyethyl)amino]-aniline, 3,4-diamino-benzoic acid,    3,4-dihydro-6-hydroxy-1,4 (2H)-benzoxazine, 6-amino-3,4-dihydro-1,4    (2H)-benzoxazine, 2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene,    2,4-diamino-1-(2-hydroxyethoxy)-5-methyl-benzene,    4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxy-benzene    2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxy-benzene,    3,4-dihydro-6-hydroxy-1,4 (2H)-benzoxazine, 6-amino-3,4-dihydro-1,4    (2H)— benzoxazine,-   di- or trihydroxybenzene derivatives such as resorcine,    resorcinmonomethylether, 2-methylresorcine, 5-methylresorcine,    2,5-dimethylresorcine, 1-chloro-2,4-dihydroxy-benzene,    2-chlororesorcine, 4-chlororesorcine,    2,6-dihydroxyethylaminotoluene,    1,2-dichlor-3,5-dihydroxy-4-methyl-benzene,    1,5-dichlor-2,4-dihydroxy-benzene, 1,3-di-hydroxy-2-methyl-benzene,    pyrogallol and 1,2,4-trihydroxybenzene,-   pyridine derivatives such as 2,6-diamino-pyridine,    2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine,    2-amino-5-chloro-3-hydroxypyridine,    5-amino-4-chloro-2-methyl-phenol, 3-diamino-6-methoxy-pyridine,    3-amino-2-methylamino-6-methoxypyridine,    2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine,    2,6-diamino-pyridine, 2,3-diamino-6-methoxypyridine,    2,6-diamino-3,5-dimethoxy-pyridine, and    3,5-diamino-2,6-dimethoxypyridine,-   naphthaline derivatives such as 1-naphthol, 2-methyl-1-naphthol,    2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol,    1,5-dihydroxynaphthaline, 1,6-dihydroxy-naphthaline,    1,7-dihydroxynaphthaline, 1,8-dihydroxynaphthaline,    2,7-dihydroxy-naphthaline and 2,3-dihydroxynaphthaline,    2-methyl-1-naphthol-acetat,-   morpholine derivatives such as 6-hydroxybenzomorpholine and    6-aminobenzo-morpholine,-   chinoxaline derivatives such as    6-methyl-1,2,3,4-tetrahydrochinoxaline,-   pyrazol derivatives such as -phenyl-3-methylpyrazol-5-one,    3-methyl-1-phenyl-5-pyrazolone,-   indol derivatives such as 4-hydroxyindol, 5-hydroxy-indol,    6-hydroxyindol and 7-hydroxyindol, 2,3-indolindione,    5,6-dihydroxy-indol, 5,6-dihydroxy-indoline,-   methylendioxybenzene derivates such as    1-hydroxy-3,4-methylendioxybenzene, 1-amino-3,4-methylendioxybenzene    and 1-(2′-hydroxyethyl)-amino-3,4-methylen-dioxybenzene,    3,4-methylendioxy-phenol, 3,4-methylendioxy-aniline,    5-[(2-hydroxy-ethyl)amino]-1,3-benzodioxol,    6-brom-1-hydroxy-3,4-methylendioxy-benzene, or-   cationic coupler compounds as described in FR 2 794 644, especially    on page 11, line 20 to page 15, line 34, and on page 17, lines 4 to    12, page 178, line 33 to page 18, line 24.

More especially preferred coupler compounds are toluene-2,5-diaminesulfate, 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthaline,3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridin,resorcinol, 4-chlororesorcine, 2-chloro-6-methyl-3-aminophenol,2,6-di-hydroxyethylaminotoluene, 2-methyl-5-dihydroxyethylaminophenol,2,4-diaminophenoxy-ethylol hydrochloride, 2-methylresorcine,5-methylresorcine, 2,5-dimethylresorcine, 3,4-methylenedioxyphenol,2-amino-4-hydroxyethylaminoanisole sulfate,2,6-di-(beta-hydroxy-ethylamino)-toluene, 4-amino-2-hydroxytoluene,6-hydroxyindol, 2-amino-3-hydroxypyridine,2,6-dimethoxy-3,5-pyridinediamine hydrochloride and2,6-dihydroxy-3,4-dimethylpyridine.

Most preferred coupler compounds are 2-chloro-6-methyl-3-aminophenol,5-amino-2-methylphenol, 2-amino-3-hydroxypyridine,2,6-di-(beta-hydroxyethylamino)-toluol, 2-methylresorcine and1-naphthol.

The developer/-coupler combination 2,4,5,6-Tetraminopyrimidine and2-Methylresorcine are preferred for assessing of red shades, or

-   p-Toluenediamine and 4-Amino-2-hydroxytoluene are preferred for    assessing of blue-violet shades, or-   p-Toluenediamine and 2-Amino-4-hydroxyethylaminoanisole are    preferred for assessing of blue shades, or-   p-Toluenediamine and 2,4-Diamino-phenoxyethynol are preferred for    assessing of blue shades, or-   3-Methyl-4-aminophenol and 4-Amino-2-hydroxytlouene are preferred    for assessing of orange shades, or-   p-Toluenediamine and resorcine are preferred for assessing of    brown-green shades, or-   p-Toluenediamine and 1-Naphthol are preferred for assessing of    blue-violet shades, or-   p-Toluenediamine and 2-methylresorcine are preferred for assessing    of brown-gold shades.

Further, the colouring method according to the present invention mayalso contain autooxidizable compounds, such as, for example benzene,indol, or indoline, especially 5,6-dihydroxyindol or5,6-dihydroxyindoline derivatives as described in WO 99/20234,especially on page 26, line 10 to page 28, line 15, or in WO 00/28957 onpage 2, third paragraph.

Preferred autooxidizable benzene derivatives are:

-   1,2,4-trihydroxybenzene, 1-methyl-2,4,5-trihydroxybenzene,    2,4-diamnio-6-methylphenol, 2-amino-4-methylaminophenol,    2,5-diamino-4-methyl-phenol, 2,6-diamino-4-diethylamino-phenol,    2,6-diamino-1,4-dihydroxybenzen, and the salts of these compounds,    which are accessible with acid.

Preferred autooxidizable indol derivatives are:

-   5,6-dihydroxyindol, 2-methyl-5,6-dihydroxyindol,    3-methyl-5,6-dihydroxyindole, 1-methyl-5,6-dihydroxyindol,    2,3-dimethyl-5,6-dihydroxyindol, 5-methoxy-6-dihydroxyindol,    5-acetoxy-6-hydroixyindol, 5,6-diacetoxyindol, acid of    5,6-dihydroxyindol-2-carbonacid, and the salts of these compounds,    which are accessible with acid.

Preferred autooxidizable indoline derivatives are:

-   5,6-dihydroxyindoline, 1-methyl-5,6-dihydroxyindoline,    1-ethyl-5,6-dihydroxyindoline, and the salts of these compounds,    which are accessible with acid. The colouring method according to    the present invention also concerns the joint use of at least two    different developers and at least one coupler compound, or    combinations of at least two different couplers and at least one    developer compound. Such combinations are for example described in    German Patent Application 197 172 24, especially on page 3, line 31    to page 5, line 8.

In addition, the colouring method according to the present invention mayalso contain naturally occurring dyes, such as, for example, henna red,henna neutral, henna black, camomile blossom, sandalwood, black tea,Rhamnus frangula bark, sage, campeche wood, madder root, catechu, sedreand alkanet root. Such colouring methods are described, for example, inEP-A-404 868, especially on page 3, line 55 to page 4, line 9.

One further embodiment of the present invention concerns formulations,which are used for the colouration of keratin fibres, especially humanhair. The formulations are applicable on human hair in differenttechnical forms. The specific technical form may be chosen in view ofthe envisaged application and/or dye or dye composition. Technical formsof formulation are for example a solution, especially a thickened wateryor watery alcoholic solution, a cream, foam, a gel, or an emulsion.

Preferred forms of formulations are ready to use compositions or amulti-compartment dyeing device or ‘kit’ or any of the multi-compartmentpackaging systems with compartments as described for example asdescribed in U.S. Pat. No. 6,190,421, column 2, lines 16 to 31.

The colouring compositions for carrying out the method according to theinvention may furthermore comprise any active ingredient, additive oradjuvant known for such preparations.

Adjuvants that are suitable for such formulations are in generalcustomary in the field hair-colouring, such as for example surfactantsor tensides, solvents, bases, acids, perfumes, polymeric adjuvant,thickeners and light stabilisers.

Suitable combinations of the colouring compositions for carrying out themethod according to the invention with adjuvant used in the colouring ofhair, for example with

-   -   combination of direct dyes with oxidizing agents to achieve        lightened colouration; wherein oxidizing agents especially        described in WO 97/20545, especially page 9, lines 5 to 9,    -   combination of direct dyes and/or an oxidation dye and oxidizing        agents in the form of permanent-wave fixing solution, especially        oxidizing agents as described in DE-A-19 713 698, especially        page 4, lines 52 to 55, or EP-A-1 062 940, especially page 6,        lines 41 to 47, (and in the equivalent WO 99/40895),    -   oxidation dyes in the presence of oxidoreductase enzyme, as        described in WO 99/17730, especially page 4, line 11 to page 13,        line 28, and WO 99/36034, especially pages 3 to 15,    -   combination of cationic dyes with polyols or polyethers; polyols        or polyethers as described in EP-A-962 219, especially page 27,        lines 14 to 38,    -   thickening polymers, as described in EP-A-970 684, especially        page 48, line 16 to page 51, line 4,    -   sugar-containing polymers, as described in EP-A-970 687,        especially page 28, line 17 to page 29, line 23,    -   quaternary ammonium salts, as described in WO 00/10517,        especially page 44, line 16 to page 46, line 23,    -   anionic surfactants, as described in WO 00/10518, especially        page 45, line 11 to page 48, line 3,    -   non-ionic surfactants, as described in WO 00/10519, especially        page 45, line 11 to page 50, line 12, or    -   silicones, as described in WO 00/12057, especially page 45, line        9 to page 55, line 2.    -   oxidative agent or laser and direct dyes, as described in EP-920        856, especially on page 2, line 31 to page 53 line 36, and on        page 49, line 38 to page 50, line 41, with direct dyes as        described on page 3, line 54 to page 48, line 52, or    -   direct dyes in the presence of cationic amphotere, substantive        polymer, as described in EP-953 334, especially on page 2, line        39 to page 7, line 44, with direct dyes as described on page 8,        line 54 to page 27, line 16, and polymers as described on page        27, line 17 to page 30, line 14, or    -   direct dyes formulations with polymer thickener on the basis of        acrylic acid, as described in EP-970 685, especially on page 2,        line 39 to page 10, line 1, with direct dyes as described on        page 10, line 7 to page 48, line 15, with polymers as described        on page 48, line 17 to page 49, line 28.

The colouring composition for carrying out the method according to theinvention in many cases comprise at least one surfactant, there beingsuitable in principle anionic and also zwitterionic, ampholytic,non-ionic and cationic surfactants. In many cases, however, it hasproved advantageous to select the surfactants from anionic, zwitterionicand non-ionic surfactants.

Anionic surfactants suitable for use in the colouring compositions forcarrying out the method according to the invention include all anionicsurface-active substances that are suitable for use on the human body.Such substances are characterised by an anionic group that imparts watersolubility, for example a carboxylate, sulfate, sulfonate or phosphategroup, and a lipophilic alkyl group having approximately from 10 to 22carbon atoms. In addition, glycol or polyglycol ether groups, ester,ether and amide groups and also hydroxy groups may be present in themolecule. The following are examples of suitable anionic surfactants,each in the form of sodium, potassium or ammonium salts or mono-, di- ortri-alkanolammonium salts having 2 or 3 carbon atoms in the alkanolgroup:

-   -   linear fatty acids having from 10 to 22 carbon atoms (soaps),    -   ether carboxylic acids of formula R—O—(CH₂—CH₂—O)_(x)—CH₂—COOH,        in which R is a linear alkyl group having from 10 to 22 carbon        atoms and x=0 or from 1 to 16,    -   acyl sarcosides having from 10 to 18 carbon atoms in the acyl        group,    -   acyl taurides having from 10 to 18 carbon atoms in the acyl        group,    -   acyl isothionates having from 10 to 18 carbon atoms in the acyl        group,    -   sulfosuccinic mono- and di-alkyl esters having from 8 to 18        carbon atoms in the alkyl group and sulfosuccinic        monoalkylpolyoxyethyl esters having from 8 to 18 carbon atoms in        the alkyl group and from 1 to 6 oxyethyl groups,    -   linear alkane sulfonates having from 12 to 18 carbon atoms,    -   linear α-olefin sulfonates having from 12 to 18 carbon atoms,    -   α-sulfo fatty acid methyl esters of fatty acids having from 12        to 18 carbon atoms,    -   alkyl sulfates and alkyl polyglycol ether sulfates of formula        R′—O(CH₂—CH₂—O)_(x)—SO₃H, in which R′ is a preferably linear        alkyl group having from 10 to 18 carbon atoms and x′=0 or from 1        to 12,    -   mixtures of surface-active hydroxysulfonates according to DE-A-3        725 030, especially page 3, lines 40 to 55,    -   sulfated hydroxyalkylpolyethylene and/or        hydroxyalkylenepropylene glycol ethers according to DE-A-3 723        354, especially page 4, lines 42 to 62,    -   sulfonates of unsaturated fatty acids having from 12 to 24        carbon atoms and from 1 to 6 double bonds according to DE-A-3        926 344, especially page 2, lines 36 to 54,    -   esters of tartaric acid and citric acid with alcohols which are        addition products of approximately from 2 to 15 molecules of        ethylene oxide and/or propylene oxide with fatty alcohols having        from 8 to 22 carbon atoms, or    -   anionic surfactants, as described in WO 00/10518, especially        page 45, line 11 to page 48, line 3.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ethersulfates and ether carboxylic acids having from 10 to 18 carbon atoms inthe alkyl group and up to 12 glycol ether groups in the molecule, andalso especially salts of saturated and especially unsaturatedC₈-C₂₂carboxylic acids, such as oleic acid, stearic acid, isostearicacid and palmitic acid.

Surface-active compounds that carry at least one quaternary ammoniumgroup and at least one —COO⁽⁻⁾ or —SO₃ ⁽⁻⁾ group in the molecule aretermed zwitterionic surfactants. Zwitterionic surfactants that areespecially suitable are the so-called betaines, such as theN-alkyl-N,N-dimethylammonium glycinates, for examplecocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyl-dimethylammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having from 8 to 18carbon atoms in the alkyl or acyl group and alsococoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferredzwitterionic surfactant is the fatty acid amide derivative known by theCTFA name cocoamidopropyl betaine.

Ampholytic surfactants are to be understood as meaning surface-activecompounds that, in addition to a C₈-C₁₈-alkyl or -acyl group, contain atleast one free amino group and at least one —COOH or —SO₃H group in themolecule and are capable of forming internal salts. Examples of suitableampholytic surfactants include N-alkylglycines, N-alkylpropionic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl-glycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids, each having approximately from 8 to 18 carbon atoms in the alkylgroup. Ampholytic surfactants to which special preference is given areN-cocoalkyl-aminopropionate, cocoacylaminoethylaminopropionate andC₁₂-C₁₈acylsarcosine.

Non-ionic surfactants are described in WO 00/10519, especially page 45,line 11 to page 50, line 12.

Non-ionic surfactants contain as the hydrophilic group, for example, apolyol group, a polyalkylene glycol ether group or a combination ofpolyol and polyglycol ether groups.

Such compounds are, for example:

-   -   addition products of from 2 to 30 mol of ethylene oxide and/or        from 0 to 5 mol of propylene oxide with linear fatty alcohols        having from 8 to 22 carbon atoms, with fatty acids having from        12 to 22 carbon atoms and with alkylphenols having from 8 to 15        carbon atoms in the alkyl group,    -   C₁₂-C₂₂ fatty acid mono- and di-esters of addition products of        from 1 to 30 mol of ethylene oxide with glycerol,    -   C₈-C₂₂alkyl-mono- and -oligo-glycosides and ethoxylated        analogues thereof,    -   addition products of from 5 to 60 mol of ethylene oxide with        castor oil and hydrogenated castor oil,    -   addition products of ethylene oxide with sorbitan fatty acid        esters,    -   addition products of ethylene oxide with fatty acid        alkanolamides.

Examples of cationic surfactants that can be used in the colouringcompositions for carrying out the method according to the invention areespecially quaternary ammonium compounds. Preference is given toammonium halides, such as alkyltrimethylammonium chlorides,dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides,for example cetyltrimethylammonium chloride, stearyltrimethylammoniumchloride, distearyldimethy-lammonium chloride, lauryidimethylammoniumchloride, lauryidimethylbenzylammonium chloride andtricetylmethylammonium chloride. Further cationic surfactants that canbe used in accordance with the invention are quaternised proteinhydrolysates.

-   -   Also suitable in accordance with the invention are cationic        silicone oils, such as, for example, the commercially available        products Q2-7224 (manufacturer: Dow Corning; a stabilised        trimethylsilylamodimethicone), Dow Corning 929 emulsion        (comprising a hydroxylamino-modified silicone, which is also        referred to as amodimethicone), SM-2059 (manufacturer: General        Electric), SLM-55067 (manufacturer: Wacker) and also Abil®-Quat        3270 and 3272 (manufacturer Th. Goldschmidt; diquaternary        polydimethylsiloxanes, quaternium-80), or silicones, as        described in WO 00/12057, especially page 45, line 9 to page 55,        line 2.

Alkylamidoamines, especially fatty acid amidoamines, such as thestearylamidopropyl-dimethylamine obtainable under the name Tego Amid®18, are distinguished not only by a good conditioning action but alsoespecially by their good biodegradability.

Quaternary ester compounds, so-called “esterquats”, such as the methylhydroxyalkyl-dialkoyloxyalkylammonium methosulfates marketed under thetrademark Stepantex® , are also very readily biodegradable.

An example of a quaternary sugar derivative that can be used as cationicsurfactant is the commercial product Glucquat® 100, according to CTFAnomenclature a “lauryl methyl gluceth-10 hydroxypropyl dimoniumchloride”.

The alkyl-group-containing compounds used as surfactants may be singlesubstances, but the use of natural raw materials of vegetable or animalorigin is generally preferred in the preparation of such substances,with the result that the substance mixtures obtained have differentalkyl chain lengths according to the particular starting material used.

The surfactants that are addition products of ethylene and/or propyleneoxide with fatty alcohols or derivatives of such addition products mayeither be products having a “normal” homologue distribution or productshaving a restricted homologue distribution. ‘Normal’ homologuedistribution is to be understood as meaning mixtures of homologuesobtained in the reaction of fatty alcohol and alkylene oxide usingalkali metals, alkali metal hydroxides or alkali metal alcoholates ascatalysts. Restricted homologue distributions, on the other hand, areobtained when, for example, hydrotalcites, alkali metal salts of ethercarboxylic acids, alkali metal oxides, hydroxides or alcoholates areused as catalysts. The use of products having restricted homologuedistribution may be preferred.

Examples of further active ingredients, adjuvants and additives are asfollows:

-   non-Ionic polymers, for example vinylpyrrolidone/vinyl acrylate    copolymers, polyvinyl-pyrrolidone and vinylpyrrolidone/vinyl acetate    copolymers and polysiloxanes,-   cationic polymers, such as quaternised cellulose ethers,    polysiloxanes having quaternary groups, dimethyldiallylammonium    chloride polymers, copolymers of dimethyldiallylammonium chloride    and acrylic acid, as available commercially under the name Merquat®    280 and the use of which in hair colouring is described, for    example, in DE-A-4 421 031, especially page 2, lines 20 to 49, or    EP-A-953 334, especially page 27, line 17 to page 30, line 11,    acrylamide/dimethyldiallylammonium chloride copolymers,    diethyl-sulfate-quaternised dimethylaminoethyl    methacrylate/vinylpyrrolidone copolymers,    vinylpyrrolidone/imidazolinium methochloride copolymers,-   quaternised polyvinyl alcohol,-   zwitterionic and amphoteric polymers, such as, for example,    acrylamido-propyl-trimethylammonium chloride/acrylate copolymers and    octylacrylamide/methyl methacrylate/tert-butylaminoethyl    methacrylate/2-hydroxypropyl methacrylate copolymers,-   anionic polymers, such as, for example, polyacrylic acids,    crosslinked polyacrylic acids, vinyl acetate/crotonic acid    copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl    acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl    ether/maleic anhydride copolymers and acrylic acid/ethyl    acrylate/N-tert-butyl acrylamide terpolymers,-   thickeners, such as agar, guar gum, alginates, xanthan gum, gum    arabic, karaya gum, locust bean flour, linseed gums, dextrans,    cellulose derivatives, e.g. methyl cellulose, hydroxyalkyl cellulose    and carboxymethyl cellulose, starch fractions and derivatives, such    amylose, amylopectin and dextrins, clays, e.g. bentonite or fully    synthetic hydrocolloids such as, for example, polyvinyl alcohol,-   structuring agents, such as glucose and maleic acid,-   hair-conditioning compounds, such as phospholipids, for example soya    lecithin, egg lecithin, and cephalins, silicone oils, and also    conditioning compounds, for example such as those described in    DE-A-19 729 080, especially page 2, lines 20 to 49, EP-A-834 303,    especially page 2, line 18 to page 3, line 2, or EP-A-312 343,    especially page 2, line 59 to page 3, line 11,-   protein hydrolysates, especially elastin, collagen, keratin, milk    protein, soya protein and wheat protein hydrolysates, condensation    products thereof with fatty acids and also quaternised protein    hydrolysates,-   perfume oils, dimethyl isosorbitol and cyclodextrins,-   solubilisers, such as ethanol, isopropanol, ethylene glycol,    propylene glycol, glycerol and diethylene glycol,-   anti-dandruff active ingredients, such as piroctones, olamines and    zinc Omadine,-   further substances for adjusting the pH value,-   active ingredients such as panthenol, pantothenic acid, allantoin,    pyrrolidonecarboxylic acids and salts thereof, plant extracts and    vitamins,-   cholesterol,-   light stabilisers and UV absorbers, as described, for example, in    EP-A-819 422, especially page 4, lines 34 to 37,-   consistency regulators, such as sugar esters, polyol esters or    polyol alkyl ethers,-   fats and waxes, such as spermaceti, beeswax, montan wax, paraffins,    fatty alcohols and fatty acid esters,-   fatty alkanolamides,-   polyethylene glycols and polypropylene glycols having a molecular    weight of from 150 to 50 000, for example such as those described in    EP-A-801 942, especially page 3, lines 44 to 55,-   complexing agents, such as EDTA, NTA and phosphonic acids,-   swelling and penetration substances, such as polyols and polyol    ethers, as listed extensively, for example, in EP-A-962 219,    especially page 27, lines 18 to 38, for example glycerol, propylene    glycol, propylene glycol monoethyl ether, butyl glycol, benzyl    alcohol, carbonates, hydrogen carbonates, guanidines, ureas and also    primary, secondary and tertiary phosphates, imidazoles, tannins,    pyrrole,-   opacifiers, such as latex,-   pearlising agents, such as ethylene glycol mono- and di-stearate,-   propellants, such as propane-butane mixtures, N₂O, dimethyl ether,    CO₂ and air, and also-   antioxidants,-   polyols or polyethers, as described in EP-A-962 219, especially page    27, lines 14 to 38,-   thickening polymers, as described in EP-A-970 684, especially page    48, line 16 to page 51, line 4,-   sugar-containing polymers, as described in EP-A-970 687, especially    page 28, line 17 to page 29, line 23,-   quaternary ammonium salts, as described in WO 00/10517, especially    page 44, line 16 to page 46, line 23.

In the context of the present invention, oxidizing agents are understoodto be any oxidizing agent customarily used for oxidative hair colouring,for example dilute hydrogen peroxide solutions, hydrogen peroxideemulsions or hydrogen peroxide gels, alkaline earth metal peroxides,organic peroxides, such as urea peroxides, melamine peroxides, oralkalimetalbromat fixations are also applicable if a shading powder onthe basis of semi-permanent, direct hair dyes is used.

Preferred oxidizing agent is hydrogen peroxide, preferred in about 2 to30% by weight, more preferred in 3 to 20% by weight, and most preferredin 6 to 12% by weight of the total weight of a watery composition suchas a solution, dispersion, a gel or emulsion.

The watery composition can comprise all customary components, which areused for the different applications of oxidizing agent compositions asdescribed in K. Schrader, “Grundlagen und Rezepturen der Kosmetika”, 2.Aufl. (1989), page 832-840.

Further preferred oxidizing agents are

-   -   oxidizing agents to achieve lightened colouration, as described        in WO 97/20545, especially page 9, lines 5 to 9,    -   oxidizing agents in the form of permanent-wave fixing solution,        as described in DE-A-19 713 698, especially page 4, lines 52 to        55, and lines 60 and 61 or EP-A-1 062 940, especially page 6,        lines 41 to 47, (and in the equivalent WO 99/40895).

An oxidizing agents may be present in the colouring compositions forcarrying out the method according to the invention preferably in anamount of from 0.01% to 6%, especially from 0.01% to 1%, based on thetotal dyeing composition.

Preferred catalysts are metal ions, such as for example Zn²⁺, Cu²⁺,Fe²⁺, Fe³⁺, Mn²⁺, Mn⁴⁺, Li⁺, Mg²⁺, Ca²⁺ and Al³⁺, preferably Zn²⁺, Cu²⁺and Mn²⁺.

The metal ions are applicable in any physiological suitable salts form.Preferred salts are acetate, sulfate, halogenide, lactate and tartrate.

Alkalimetalsulfits, such as sodium-, potassium-, lithium-sulfite,Alkalimetaldisulfits, such as sodium-, potassium-, lithium-disulfite,ascorbic acid, tert.-Butylhydrochinon and Ammoniumthiolactat.

In general, the coloration with an oxidative agent is conducted in thepresence of a base. Bases are for example ammonia, alkali metalcarbonates, earth metal carbonates, alkanol amines, such as for examplemono-, di- or triethanolamine, alkali metal hydroxides, earth metalhydroxides, compounds of the formula

wherein,

-   R is a propyl residue, which substituted with OH or C₁-C₄-alkyl,-   R₃, R₄, R₅ and R₆ are independently or dependently from each other    hydrogen, C₁-C₄-alkyl or hydroxy-(C₁-C₄)-alkyl.

Alkali metal is for example sodium, potassium or lithium. Earth metal isfor example magnesium or calcium.

Acids are inorganic or organic acids, such as hydrochloride, tartratacid, citric acid, ascorbine acid and phosphor acid.

The use of UV absorbers can effectively protect natural and dyed hairfrom the damaging rays of the sun and increase the wash fastness of dyedhair.

Suitable UV absorbers the colouring compositions for carrying out themethod according to the invention are:

-   -   cationic benzotriazole UV absorbers as for example described in        WO 01/36396 especially on page 1, line 20 to page 2, line 24,        and preferred on page 3 to 5, and on pages 26 to 37, or    -   cationic benzotriazole UV in combination with antioxidants as        described in WO 01/36396, especially on page 11, line 14 to page        18, or    -   UV absorbers in combination with antioxidants as described in        U.S. Pat. No. 5,922,310, especially in column 2, lines 1 to 3,    -   UV absorbers in combination with antioxidants as described in        U.S. Pat. No. 4,786,493, especially in column 1, 42 to column 2,        line 7, and preferred in column 3, 43 to column 5, line 20, or    -   combination of UV absorbers as described in U.S. Pat. No.        5,830,441, especially in column 4, lines 53 to 56, or    -   combination of UV absorbers as described in WO 01/36396,        especially on page 11, lines 9 to 13, or    -   triazine derivatives provide effective UV protection as        described in WO 98/22447, especially on page 1, line 23 to page        2, line 4, and preferred on page 2, line 11 to page 3, line 15        and most preferred on pages 6 to 7, and 12 to 16, or    -   combination of the cosmetic formulations as described in WO        98/22447 with one or more than one further UV filter as        described in the following patents:

(Abbreviations T: table, R: row, Comp: compound, Ex: compound(s) ofpatent example, p: page) EP 895776 Comp. in Rows 48-58, p 3; R 25 + 33,p 5 WO 9220690 Polymeric comp in Examples 3-6 EP 1000950 Comp. in Table1, pp 18-21 EP 1060734 T 1-3, pp 11-14 EP 1059082 Ex 1; T 1, pp 9-11 EP1008586 Ex 1-3, pp 13-15 EP 1005855 T 3, p 13 EP 1129695 Ex 1-7, pp13-14 EP 967200 Ex 2; T 3-5, pp 17-20 EP 945125 T 3 a + b, pp 14-15 EP924246 T 2, p 9 EP 911020 T 2, p 11-12 EP 916335 T 2-4, pp 19-41 EP852137 T 2, pp 41-46 EP 858318 T 1, p 6 EP 826361 T 1, pp 5-6 EP 503338T 1, pp 9-10 WO 9301164 T 1 + 2, pp 13-22 EP 823418 Ex 1-4, pp 7-8 WO9714680 Ex 1-3, p 10 EP 1027883 Compound VII, p 3 EP 832641 Ex 5 + 6 p7; t 2, p 8 U.S. Pat. No. 5338539 Ex 1-9, pp 3 + 4 EP 517103 Ex 3, 4, 9,10 pp 6-7 EP 1123934 T 3, p 10 EP 1027883 Comp I-VI, p 3 EP 969004 Ex 5,T 1, pp 6-8 U.S. Pat. No. 5801244 Ex 1-5, pp 6-7 EP 832642 Ex 22, T 3pp, 10-15; T 4, p 16 U.S. Pat. No. 5346691 Ex 40, p 7; T 5, p 8 (EP570838) EP 517104 Ex 1, T 1, pp 4-5; Ex 8, T 2, pp 6-8 WO 200149686 Ex1-5, pp 16-21 EP 944624 Ex 1 + 2, pp13-15 EP 933376 Ex 1-15, pp 10-21 EP863145 Ex 1-11, pp 12-18 EP 780382 Ex 1-11, pp 5-7 EP 626950 EP 1081140Ex 1-9, pp 11-16 WO 9217461 Ex 1-22, pp 10-20 WO 0168047 Tables on pp85-96 EP 613893 Ex 1-5 + 15, T 1, pp 6-8 EP 1064922 Compounds 1-34, pp6-14 EP 1028120 Ex 1-5, pp 5-13 EP 1008593 Ex 1-8, pp 4-5 EP 669323 Ex1-3, p 5 EP 1108712 4,5-Dimorpholino-3-hydroxypyridazine JP 2000319629CAS Regno. 80142-49-0, 137215-83-9, 307947-82-6 EP 420707 B1 Ex 3, p 13(80142-49-0) U.S. Pat. No. 5635343 EP 1167358

In addition to the triazine UV absorbers described in WO 98/22447, thecosmetic formulations can also contain one or more than one further UVprotective of the following substance classes:

-   p-aminobenzoic acid derivatives, for example 4-dimethylaminobenzoic    acid 2-ethylhexyl ester;-   salicylic acid derivatives, for example salicylic acid 2-ethylhexyl    ester;-   benzophenone derivatives, for example    2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative;-   dibenzoylmethane derivatives, for example    1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione;-   diphenylacrylates, for example 2-ethylhexyl    2-cyano-3,3-diphenylacrylate, and 3-(benzofuranyl)2-cyanoacrylate;-   3-imidazol-4-ylacrylic acid and esters;-   benzofuran derivatives, especially 2-(p-aminophenyl)benzofuran    derivatives, described in EP-A-582 189, U.S. Pat. No. 5,338,539,    U.S. Pat. No. 5,518,713 and EP-A-613 893;-   polymeric UV absorbers, for example the benzylidene malonate    derivatives described in EP-A-709 080;-   cinnamic acid derivatives, for example the 4-methoxycinnamic acid    2-ethylhexyl ester and isoamyl ester or cinnamic acid derivatives    described in U.S. Pat. No. 5,601,811 and WO 97/00851;-   camphor derivatives, for example    3-(4′-methyl)benzylidene-bornan-2-one, 3-benzyl-idenebornan-2-one,    N-[2(and 4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer,    3-(4′-trimethylammonium)-benzylidene-bornan-2-one methyl sulfate,    3,3′-(1,4-phenylenedimethine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonic    acid) and salts, 3-(4′-sulfo)benzylidene-bornan-2-one and salts;    camphorbenzalkonium methosulfate;-   hydroxyphenyltriazine compounds, for example    2-(4′-methoxyphenyl)-4,6-bis(2′-hydroxy-4′-n-octyloxyphenyl)-1,3,5-triazine;    2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;    2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-[4-(2-methoxyethyl-carboxyl)-phenylamino]-1,3,5-triazine;    2,4-bis{[4-(tris(trimethylsilyloxy-silylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;    2,4-bis{[4-(2″-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;    2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethyltrisilyl-2″-methyl-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;    2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-[4-ethylcarboxy)-phenylamino]-1,3,5-triazine;-   benzotriazole compounds, for example    2,2′-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol;-   trianilino-s-triazine derivatives, for example    2,4,6-trianiline-(p-carbo-2′-ethyl-1′-oxy)-1,3,5-triazine and the UV    absorbers disclosed in U.S. Pat. No. 5,332,568, EP-A-517 104,    EP-A-507 691, WO 93/17002 and EP-A-570 838;-   2-phenylbenzimidazole-5-sulfonic acid and salts thereof;-   methyl o-aminobenzoates;-   physical sunscreens coated or not as titanium dioxide, zinc oxide,    iron oxides, mica, MnO, Fe₂O₃, Ce₂O₃, Al₂O₃, ZrO₂. (surface    coatings: polymethylmethacrylate, methicone    (methylhydrogenpolysiloxane CAS 9004-73-3), dimethicone, isopropyl    titanium triisostearate (CAS 61417-49-0), metal soaps as magnesium    stearate (CAS 4086-70-8), perfluoroalcohol phosphate as C9-15    fluoroalcohol phosphate (CAS 74499-44-8; JP 5-86984, JP 4-330007)).    The primary particle size is an average of 15 nm-35 nm and the    particle size in dispersion is in the range of 100 nm-300 nm.-   aminohydroxy-benzophenone derivatives disclosed in DE 10011317, EP    1133980 and EP 1046391-   phenyl-benzimidazole derivatives as disclosed in EP 1167358-   The UV absorbers described in “Sunscreens”, Eds. N. J. Lowe, N. A.    Shaath, Marcel Dekker, Inc., New York and Basle or in Cosmetics &    Toiletries (107), 50ff (1992) also can be used as additional UV    protective substances.

Examples of (synergistic) combinations of UV absorbers in cosmetic orpharmaceutical preparations are also described in the following table.The combinations of UV filters are useful to protect skin, hair and/ornatural or artificial hair color (ratio of UV absorbers in columnsC1-C12). No Chemical Name CAS No. C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12UV 1 (+/−)-1,7,7-trimethyl-3-[(4- 36861-47-9 15 methylphenyl)-methylene]bicyclo [2.2.1]heptan-2-one UV 2 1,7,7-trimethyl-3- 15087-24-8(phenylmethylene)- bicyclo[2.2.1]heptan-2-one UV 3 (2-Hydroxy-4-1641-17-4 10 methoxyphenyl)(4-methylphenyl) methanone UV 42,4-dihydroxy- 131-56-6 10 benzophenone UV 5 2,2′,4,4′-tetrahydroxy-131-55-5 10 benzophenone UV 6 2-Hydroxy-4-methoxybenzophenone; 131-57-7UV 7 2-Hydroxy-4-methoxybenzophenone- 4065-45-6 5-sulfonic acid UV 82,2′-dihydroxy-4,4′- 131-54-4 10 10 dimethoxybenzo-phenone UV 92,2′-Dihydroxy-4- 131-53-3 10 methoxybenzophenone UV 10Alpha-(2-oxoborn-3- 56039-58-8 15 10 10 ylidene)toluene-4- sulphonicacid and its salts UV 11 1-[4-(1,1- 70356-09-1 15 10dimethylethyl)phenyl]-3- (4-methoxyphenyl)- propane-1,3-dione UV 12Methyl N,N,N-trimethyl-4- 52793-97-2 [(4,7,7-trimethyl-3-oxobicyclo[2,2,1]hept-2- ylidene)methyl]-anilinium sulphate; UV 223,3,5-Trimethyl 118-56-9 cyclohexyl-2-hydroxy benzoate

No Chemical Name CAS No. C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 UV 23Isopentyl p-methoxy-cinnamate 71617-10-2 10 UV 27Menthyl-o-aminobenzoate 134-09-8 UV 28 Methyl salicylate 89-46-3 15 UV29 2-Ethylhexyl 2-cyano,3,3- 6197-30-4 15 10 diphenylacrylate UV 302-ethylhexyl 4-(dimethyl- 21245-02-3 amino)benzoate UV 31 2-ethylhexyl4- 5466-77-3 20 25 50 methoxycinnamate UV 32 2-ethylhexyl salicylate118-60-5 UV 33 Benzoic acid, 4,4′,4″-(1,3,5- 88122-99-0 20 10triazine-2,4,6-triyltri- imino)tris-, tris(2-ethylhexyl) ester;2,4,6-Trianilino-(p-carbo- 2′-ethylhexyl-1′-oxi)-1,3,5- triazine UV 344-aminobenzoic acid 150-13-0 UV 35 Benzoic acid, 4-amino-, ethyl113010-52-9 ester, polymer with oxirane UV 38 2-phenyl-1H-benzimidazole-27503-81-7 15 10 10 5-sulphonic acid UV 39 2-Propenamide, N-[[4-[(4,7,7-147897-12-9 trimethyl-3-oxobicyclo- [2.2.1]hept-2-ylidene)methyl]-phenyl]methyl]-, homopolymer

No Chemical Name CAS No. C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 UV 40Triethanolamine 2174-16-5 salicylate UV 41 3,3′-(1,4-phenylene-90457-82-2 dimethylene)bis[7,7- dimethyl-2-oxo- bicyclo[2.2.1]heptane-1-methanesulfonic acid] UV 42 Titanium dioxide 13463-67-7 5 7.5 25 10 10UV 44 Zinc oxide 1314-13-2 15 10 10 UV 45 2,2′-Methylene-bis-[6-103597-45-1 15 20 20 10 10 (2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethyl- butyl)-phenol] UV 46 2,4-bis{[4-(2-ethyl-187393-00-6 10 15 15 15 10 hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl) (1,3,5)-triazine UV 47 1H-Benzimidazole-4,6-180898-37-7 15 10 disulfonic acid, 2,2′- (1,4-phenylene)bis-, disodiumsalt UV 48 Benzoic acid, 4,4′-[[6- 154702-15-5 20 15 10 10[[4-[[(1,1-dimethyl- ethyl)amino]carbonyl]- phenyl]amino]1,3,5-triazine-2,4- diyl]diimino]bis-, bis(2- ethylhexyl)ester UV 49 Phenol,2-(2H-benzotriazol- 155633-54-8 15 15 10 10 2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3- tetramethyl-1- [(trimethylsilyl)oxy]-disiloxanyl]propyl]- UV 50 alpha-(trimethylsilyl)- 207574-74-1 15 15 10omega-(trimethylsilyloxy) poly[oxy(dimethyl) silylene]-co-[oxy(methyl)(2-{p-[2,2- bis(ethoxy- carbonyl)vinyl]phenoxy}-1-methyleneethyl)silylene]- co-[oxy(methyl)(2- {p-[2,2-bis(ethoxycarbonyl)vinyl] phenoxy}prop-1- enyl)silylene] UV 51Benzenesulfonic acid, 92484-48-5 10 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1- methy-lpropyl)-, monosodium salt UV 52 Benzoic acid,2-[4- 302776-68-7 40 25 15 15 30 10 10 25 10 (diethylamino)-2-hydroxybenzoyl]-, hexyl ester UV 53 1-Dodecanaminium, N- 156679-41-3[3-[[4- (dimethylamino)benzoyl] amino]propyl]-N,N- dimethyl-, salt with4- methylbenzenesulfonic acid (1:1) UV 54 1-Propanaminium, 177190-98-6N,N,N-trimethyl-3-[(1- oxo-3-phenyl-2- propenyl)amino]-, chloride UV 551H-Benzimidazole-4,6- 170864-82-1 15 10 10 10 disulfonic acid, 2,2′-(1,4-phenylene)bis- UV 56 1,3,5-Triazine, 2,4,6- 7753-12-0 10 7.5 15 105 50 25 25 25 10 10 10 tris(4-methoxyphenyl)- UV 57 1,3,5-Triazine,2,4,6- 208114-14-1 15 10 10 tris[4-[(2- ethylhexyl)oxy]phenyl]- UV 581-Propanaminium, 3- 340964-15-0 [[3-[3-(2H- [[3-[3-(2H-benzotriazol-2-yl)-5- (1,1-dimethylethyl)-4- hydroxyphenyl]-1-oxopropyl]amino]- N,N-diethyl-N-methyl-, methyl sulfate (salt) UV 592-Propenoic acid, 3- 104-98-3 (1H-imidazol-4-yl)- UV 60 Benzoic acid, 2-94134-93-7 hydroxy-, [4-(1- methylethyl)phenyl]methyl ester UV 611,2,3-Propanetriol, 1- 136-44-7 (4-aminobenzoate) UV 62 Benzeneaceticacid, 4732-70-1 3,4-dimethoxy-a-oxo- UV 63 2-Propenoic acid, 2-5232-99-5 cyano-3,3-diphenyl-, ethyl ester

The following examples C1-C12 illustrate combinations of UV absorbersand antioxidants in cosmetic preparations which are useful to protecthair and natural or artificial hair color (% by weight, based on thetotal weight of the composition). Compound (CAS No.) C1 C2 C3 C4 C5 C6C7 C8 C9 C10

2 3 4 1 2 3 1 2 2.5 1 BENZENESULFONIC ACID, 3- 1 1(2H-BENZOTRIAZOL-2-YL)-4- HYDROXY-5-(1-METHY- LPROPYL)-, MONOSODIUM SALT(92484-48-5) PROPYL GALLATE (121-79-9) 1 0.5 1 1N-[3-(3,5-DI-TERT-BUTYL-4- 2 1 1 2 HYDROXYPHENYL)PROPIONY L] SULFANILCACID (OR SALTS E.G. WITH SODIUM) BENZYLIDENE MALONATE 2 0.2 POLYSILOXANE(207574-74-1) DROMETRIZOLE TRISILOXANE 1 0.5 (155633-54-8) DIETHYLHEXYLBUTAMIDO 0.2 TRIAZONE (154702-15-5) PHENOL, 2,2′-[6-(4- 0.2METHOXYPHENYL)-1,3,5- TRIAZINE-2,4-DIYL]BIS[5-[(2- ETHYLHEXYL)OXY]-(187393-00-6) 1H-BENZIMIDAZOLE-4,6- 1 DISULFONIC ACID, 2,2′-(1,4-PHENYLENE)BIS-, DISODIUM SALT (180898-37-7)

Compound (CAS No.) C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 BIS-BENZOTRIAZOLYL 0.5TETRAMETHYLBUTYL-PHENOL (103597-45-1) TEREPHTHALYLIDENE 0.5 DICAMPHORSULFONIC ACID (90457-82-2) POLYACRYLAMIDOMETHYL 1 BENZYLIDENE CAMPHOR(113783-61-2) PHENYLBENZIMIDAZOLE 1 SULFONIC ACID (27503-81-7)ETHYLHEXYL METHOXY- 0.5 0.5 0.2 0.5 CINNAMATE (5466-77-3) OCTOCRYLENE(6197-30-4) 0.5 0.5 CAMPHOR BENZALKONIUM 0.5 0.1 METHOSULFATE(52793-97-2) BUTYL METHOXYDIBENZOYL- 1 METHANE (70356-09-1)BENZOPHENONE-3 (131-57-7) 0.1 0.1 0.5 0.2 BENZOPHENONE-4 (4065-45-6) 0.10.1 0.5 1-DODECANAMINIUM, N-[3-[[4- 1 (DIMETHYLAMINO)-BENZOYL]AMINO]PROPYL]-N,N-DIMETHYL-, SALT WITH 4- METHYLBENZENESULFONIC ACID(156679-41-3) 1-PROPANAMINIUM, N,N,N- 1 1 TRIMETHYL-3-[(1-OXO-3-PHENYL-2-PROPENYL)AMINO]-, CHLORIDE (177190-98-6) 3-BENZYLIDENE CAMPHOR0.5 (15087-24-8) 4-METHYLBENZYLIDENE 0.2 CAMPHOR (36861-47-9)BENZYLIDENE CAMPHOR 1 SULFONIC ACID (56039-58-8)

Preference is given to the use of mixing ratios of triazine derivativesof formula 1-8/further light-protective agents from 1:99 to 99:1,especially from 1:95 to 95:1 and preferably from 10:90 to 90:10, basedon weight. Of special interest are mixing ratios of from 20:80 to 80:20,especially from 40:60 to 60:40 and preferably approximately 50:50. Suchmixtures can be used, inter alia, to improve solubility or increase UVabsorption.

Synergistic effects are observed when UV absorbers are used incombination with antioxidants. Examples of antioxidants that can be usedare listened in WO 01/36396 (pages 11-18), U.S. Pat. No. 5,922,310 andU.S. Pat. No. 4,786,493.

Examples of UV absorbers used in addition to the uncharged and cationicbenzotriazole UV absorbers in the formulations without limitation tothose listed in the following might be benzophenone-type substances suchas benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-4,benzophenone-5 (sodium salt) or benzotriazol-type substances such asbenzenesulfonic acid,3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-, monosodium salt;2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl-phenol;2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-phenol, branched and linear.Typical ingredients in the oil phase of emulsions (water in oil, oil inwater or triple emulsion) or used in hair oils can be chosen from thefollowing substance groups without limiting the kind of lipophilicingredients to those substances:

Suitable cosmetic preparations may contain usually from 0.05 to 40% byweight, preferably from 0.1 to 20% by weight, based on the total weightof the composition, of one or more UV absorbers.

Preferred are the cosmetic preparations contain at least one triazinederivative UV absorber, for example, from 0.1 to 40% by weight,preferably from 0.1 to 20% by weight and especially from 0.5 to 10% byweight, based on the total weight of the composition, and the cosmeticpreparations contain at least one cationic benzotriazole from 0.05-20%by weight, preferred from 0.1-20% by weight, based on the total weightof the composition. Typical cosmetic formulations containing unchargedand/or cationic benzotriazoles and/or antioxidants alone or incombinations are rinse-off products (e.g. shampoos, hair rinses,conditioners etc.), Suitable cosmetic formulations are:

-   -   cosmetic hair-treatment preparations, e.g. hair-washing        preparations in the form of shampoos and conditioners, hair-care        preparations, e.g. pre-treatment preparations or leave-on        products such as sprays, creams, gels, lotions, mousses and        oils, or hair tonics, styling creams, styling gels, pomades,        hair rinses, treatment packs, intensive hair treatments,        hair-structuring preparations, e.g. hair-waving preparations for        permanent waves (hot wave, mild wave, cold wave),        hair-straightening preparations, liquid hair-setting        preparations, hair foams, hairsprays, bleaching preparations,        e.g. hydrogen peroxide solutions, lightening shampoos, bleaching        creams, bleaching powders, bleaching pastes or oils, temporary,        semi-permanent or permanent hair colourants, preparations        containing self-oxidising dyes, or natural hair colourants, such        as henna or camomile.

The final formulations listed may exist in a wide variety ofpresentation forms, for example:

-   -   in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W        or PIT emulsion and all kinds of microemulsions,    -   in the form of a gel,    -   in the form of an oil, a cream, milk or lotion,    -   in the form of a powder, a lacquer, a tablet or make-up,    -   in the form of a stick,    -   in the form of a spray (spray with propellant gas or pump-action        spray) or an aerosol,    -   in the form of a foam, or    -   in the form of a paste.

Of special importance as cosmetic preparations for the hair are theabove-mentioned preparations for hair treatment, especially hair-washingpreparations in the form of shampoos, hair conditioners, hair-carepreparations, e.g. pre-treatment preparations, hair tonics, stylingcreams, styling gels, pomades, hair rinses, treatment packs, intensivehair treatments, hair-straightening preparations, liquid hair-settingpreparations, hair foams and hairsprays. Of special interest arehair-washing preparations in the form of shampoos.

A shampoo has, for example, the following composition: from 0.01 to 5%by weight of a UV absorber according to the invention, 12.0% by weightof sodium laureth-2-sulfate, 4.0% by weight of cocoamidopropyl betaine,3.0% by weight of sodium chloride, and water ad 100%.

Any known process suitable for the preparation of microparticles can beused for the preparation of the micronised UV absorbers, for example:

-   -   wet-grinding with a hard grinding medium, for example zirconium        silicate and a protective surfactant or a protective polymer in        water or in a suitable organic solvent;    -   spray-drying from a suitable solvent, for example aqueous        suspensions or suspensions containing organic solvents, or true        solutions in water, ethanol, dichloroethane, toluene or        N-methylpyrrolidone etc.;    -   by the expansion according to the RESS process (Rapid Expansion        of Supercritical Solutions) of supercritical fluids (e.g. CO₂)        in which the UV filter or filters is/are dissolved, or the        expansion of fluid carbon dioxide together with a solution of        one or more UV filters in a suitable organic solvent;    -   by reprecipitation from suitable solvents, including        supercritical fluids (GASR process=Gas Anti-Solvent        Recrystallisation/PCA process=Precipitation with Compressed        Anti-solvents).

As grinding apparatus for the preparation of the micronised organic UVabsorbers there may be used, for example, a jet mill, ball mill,vibratory mill or hammer mill, preferably a high-speed mixing mill. Thegrinding is preferably carried out with a grinding aid, for example analkylated vinylpyrrolidone polymer, a vinylpyrrolidone/vinyl acetatecopolymer, an acyl glutamate, an alkyl polyglucoside, ceteareth-25 or aphospholipid.

The micronised UV absorbers so obtained usually have an average particlesize that is from 0.02 to 2 μm, preferably from 0.05 to 1.5 μm, and moreespecially from 0.1 to 1.0 μm.

The UV absorbers can also be used dry in powder form. For that purposethe UV absorbers are subjected to known grinding methods, such as vacuumatomization, countercurrent spray-drying etc. Such powders have aparticle size of from 0.1 μm to 2 μm. To avoid the occurrence ofagglomeration, the UV absorbers can be coated with a surface-activecompound prior to the pulverisation process, for example with ananionic, non-ionic or amphoteric surfactant, e.g. a phospholipid or aknown polymer, such as PVP, or an acrylate. The colouring compositionsfor carrying out the method according to the invention may furthercomprise antimicrobial agents.

Typical antimicrobial preservatives and antimicrobial actives used informulations (in most cases the INCI name of the antimicrobialsubstances is mentioned): formaldehyde and paraformaldehyde, hydroxybiphenyls and its salts such as ortho-phenylphenol, zinc pyrithion,chlorobutanol, hydroxy benzoic acids and their salts and esters such asmethyl paraben, ethyl paraben, propyl paraben, butyl paraben, dibromohexamidine and its salts including isothionate(4,4′-hexamethylenedioxy-bis(3-bromo-benzamidine) and4,4′-hexamethylenedioxy-bis(3-bromo-benzamidinium2-hydroxyethanesulfonate), mercury, (aceto-O)phenyl (especially phenylmercuric acetate) and Mercurate(2-),(orthoborate(3-)-O)phenyl,dihydrogene (especially phenyl mercuric borate),1,3-bis(2-ethylhexyl)-hexahydro-5-methyl-5-pyrimidine (Hexetidin),5-bromo-5-nitro-1,3-dioxan, 2-bromo-2-nitro-1,3-propandiol,2,4-dichlorobenzyl alcohol, 3,4,4′ trichlorocarbanilide(Trichlorcarban), p-chloro-m-cresol, 2,4,4′-trichloro 2-hydroxydiphenylether (triclosan), 4,4′-dichloro 2-hydroxy diphenylether,4-chloro-3,5-dimethylphenol (Chloroxylenol), imidazolidinyl urea,poly-(hexamethylene biguanide) hydrochloride, 2-phenoxy ethanol(phenoxyethanol), hexamethylene tetramine (Methenamine),1-(3-chloroallyl)-3,5,7-triaza-1-azonia-adamantanchloride (Quaternium15), 1-(4-chlorophenyoxy)-1-(1-imidazolyl)3,3-dimethyl-2-butanone(Climbazole), 1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione(DMDM hydantoin), benzyl alcohol, 1,2-dibromo-2,4-dicyano butane, 2,2′methylene-bis(6-bromo-4-chloro phenol) (bromochlorophene),methylchloroisothiazolone, methylisothiazolone, octylisothiazolone,benzylisothiazolone, 2-benzyl-4-chlorophenol (Chlorophenone),chloracetamide, chlorhexidine, chlorhexidine acetate, chlorhexidinegluconate, chlorhexidine hydrochloride, 1-phenoxy-propane-2-ol(phenoxyisopropanol), 4,4-dimethyl-1,3-oxazolidine (dimethyloxazolidine), diazolidinyl urea, 4,4′-hexamethylenedioxybisbenzamidineand 4,4′-hexamethylenedioxybis(benzamidinium-2-hydroxyethanesulfonate),glutaraldehyde (1,5-pentanedial), 7-ethylbicyclooxazolidine,3-(4-chlorophenoxy)-1,2-propandiol (chlorophenesin),phenylmethoxymethanol and ((phenylmethoxy)methoxy)-methanol(benzylhemiformal), N-alkyl(C12-C22)trimethyl ammoniumbromide and-chloride (cetrimonium bromide, cetrimonium chloride),benzyl-dimethyl-(4-(2-(4-(1,1,3,3-tetramethylbutyl)-phenoxy)-ethoxy)-ethyl)-ammoniumchloride(benzethonium chloride), Alkyl-(C₈-C₁₈)-dimethyl-benzylammoniumchloride, -bromide and saccharinate (benzalkonium chloride, benzalkoniumbromide, benzalkonium saccharinate), benzoic acid and its salts andesters, propionic acid and its salts, salicylic acid and its salt,sorbic acid and its salts, sodium iodiate, inorganic sulfites andbisulfites such as sodium sulfite, dehydroacetic acid, formic acid,mercurate(1-ethyl)₂-mercaptobenzoate(2-)-O,S-, hydrogene (Thiomersal orThiomerosal), 10-undecylenic acid and its salts, octopirox (piroctoneolamine), sodium hydroxy methyl-aminoacetate (sodiumhydroxymethylglycinate), 3-iodo-2-propynyl butylcarbamate,10-undecylenic acid, sulfur.

Combinations with natural antimicrobials or chemically modified naturalsubstances with antimicrobial activities such as chitosans and chitosanderivatives, farnesol, plant extracts such as clove oil, blue cypres oiletc. can be also used.

For use on human hair, the dyeing compositions can usually beincorporated into an aqueous cosmetic carrier. Suitable aqueous cosmeticcarriers include, for example, creams, sprays, emulsions, gels, powdersand also surfactant-containing foaming solutions, e.g. shampoos or otherpreparations, that are suitable for use on keratin-containing fibers.Such forms of use are described in detail in Research Disclosure 42448(August 1999). If necessary, it is also possible to incorporate thedyeing compositions into anhydrous carriers, as described, for example,in U.S. Pat. No. 3,369,970, especially column 1, line 70 to column 3,line 55. The dyeing compositions according to the invention are alsoexcellently suitable for the colouring method described in DE-A-3 829870 using a colouring comb or a colouring brush.

Further carriers for dying compositions are for example described in“Dermatology”, edited by Ch. Culnan, H. Malbach, Verlag Marcel DekkerInc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of HairCare, chapter 7, pages 248-250, especially on page 243, line 1 to page244, line 12.

Suitable formulations of cationic dyes, which can be used in thecolouring compositions for carrying out the method according to theinvention are described for example in

-   -   in WO 95/01772, especially on page 11, line 29 to page 12, line        7, or    -   in WO 01/66646, especially on page 7, line 1 to page 22, and        preferred from page 16, line 20 to page 22, or    -   direct dyes as described in DE-A-19 713 698, especially page 3,        line 51 to page 4, line 29 and page 4, line 65 to page 5, line        60, or    -   direct dyes and oxidizing agent as described in WO 97/20545,        especially on page 9, line 1 to page 11, line 4, in particular        on page 11, line 6 to page 13, line 19.

Preferred formulations of cationic dyes with other dyes, which can beused in the colouring compositions for carrying out the method accordingto the invention, are:

-   -   combinations of Pyrazolo-[1,5-a]-pyrimidines with at least one        cationic dye as described in EP 998,908, especially on page 47,        line 3 to page 49, line 26, and preferred on page 51, line 4 to        page 52, line 5, or    -   combinations of cationic dyes as described in FR-2788432,        especially on page 53, line 1 to page 63, line 23, especially a        combination of cationic dyes with Arianors in FR-2788432,        especially on pages 51 to 52, or especially a combination with        at least one Basic Brown 17, Basic brown 16, Basic Red 76 and        Basic Red 118, and/or at least one Basic Yellow 57, and/or at        least one Basic Blue 99, or    -   combinations of direct dyes and/or an oxidation dye and        oxidizing agents in the form of permanent-wave fixing solution,        especially with direct dyes as described in DE-A-19 713 698,        especially page 4, line 65 to page 35, line 59, or    -   combinations of cationic dyes and an oxidation dye of the        developer compound type and oxidizing agents as described in EP        850 638, especially on page 2, lines 3 to 12 and line 30 to page        14, and page 28, line 35 to page 30, line 20, preferred on page        30, line 25 to page 32, line 30, or    -   ready-to-use dyeing compositions and multicompartment device for        dyeing keratin fibers comprising combinations of an        extemporaneous mixture of a composition (A) containing one or        more oxidation dye precursors and optionally one or more        couplers, and of a composition (B), in powder form, containing        one or more direct dye, preferably cationic, optionally        dispersed in an organic pulverulent excipient and/or a mineral        pulverulent excipient, and a composition (C) containing one or        more oxidizing agent as described in U.S. Pat. No. 6,190,421,        especially in column 2, line 20 to line 31 in column 7, line 15        to column 8, line 43, and preferably in column 8, line 55 to        column 9, line 56, and preferably with direct dyes as described        in column 5, line 30 to column 7, line 14, or    -   a ready-to-use composition comprising, at least one oxidation        base, at least one cationic direct dye and at least one enzyme        of 2-electron oxidoreductase type in the presence of at least        one donor for the said enzyme as described in U.S. Pat. No.        6,228,129, especially in column 2, line 16 to column 25, line        55, and a multi-compartment dyeing device as described in column        26, lines 13 to 24, especially in column 26, line 26 to column        27, line 9, or    -   a ready-to-use composition comprising compositions of at least        one direct cationic dye and at least one nitrated benzene dye as        described in WO 99/20235 especially on page 1, line 25 to page        8, line 5, and on page 30, line 17 to page 34 line 25, with        cationic direct dyes as described on page 8, line 12 to page 25        line 6, and a multi-compartment dyeing device as described on        page 35, lines 21 to 27, especially on page 36, line 1 to page        37, or    -   a ready-to-use composition or a multi-compartment dyeing device        comprising compositions of at least one direct cationic dye and        at least one autooxidisable oxidation dye, especially benzene,        indol and indoline derivatives as described in WO 99/20234,        especially on page 26, line 5 to page 32, line 18, or    -   oxidation dyeing compositions of at least one direct dye and at        least one meta-Aminophenol derivative and at least one developer        compound and an oxidizing agent as described in EP 850 636,        especially on page 18, line 1 to page 22, line 11, or    -   oxidation dyeing compositions of at least one direct dye and at        least one developer compound selected from the group of        para-Phenylenediamine derivatives and Bis-Phenylalkylenediamine        and, and at least one coupler compound selected from the group        of meta-Diphenols and an oxidizing agent, as described in        EP-A-850 637, especially on page 19, line 24 to page 22, line        57,    -   cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives,        as described in EP 998 908, especially on page 47, line 25 to        page 50, line 29, or    -   oxidative dye precursors (unsaturated aldehyde and coupler        compounds), as described in German Patent Application 197 172        24, especially on page 3, line 36 to page 9 line 64.

Cationic dyes may be present in the colouring compositions for carryingout the method according to the invention preferably in an amount offrom 0.001% to 5%, especially from 0.01% to 1%, based on the totaldyeing composition.

The pH value of the ready-to-use dyeing preparations is usually from 2to 11, preferably from 5 to 10.

The constituents of the aqueous carrier are used in the colouringcompositions for carrying out the method according to the invention inthe amounts customary for that purpose; for example emulsifiers may beused in concentrations of from 0.5 to 30% by weight and thickeners inconcentrations of from 0.1 to 25% by weight of the total dyeingcomposition.

If direct dyes are used together with oxidation dyes, they may be storedseparately or together.

It is preferred to store the oxidation dyes and direct dyes, which arenot stable to reduction, separate

They may be stored in a liquid to paste-like preparation (aqueous ornon-aqueous) or in the form of a dry powder.

When the dyes and adjuvants are stored together in a liquid preparation,the preparation should be substantially anhydrous in order to reducereaction of the compounds.

When they are stored separately, the reactive components are intimatelymixed with one another only immediately before use. In the case of drystorage, before use a defined amount of hot (from 50 to 80° C.) water isusually added and a homogeneous mixture prepared.

One preferred method of applying direct dyes containing formulations onhair is by using a multi-compartment dyeing device or “kit” or any othermulti-compartment packaging system, as described for example in WO97/20545 on page 4, line 19 to line 27.

The colouring compositions for carrying out the method according to theinvention may combined with a suitable ready-to-use composition for theoxidation dyeing of keratin fibers, in particular human keratin,comprising an oxidizing agent, at least one direct dye and at least oneoxidation dye precursor, as described in U.S. Pat. No. 6,190,421, incolumn 1, line 65 to column 3, line 65, especially in column 10, line 62to column 12, line 65.

Preferably, such a ready-to-use composition is prepared according to afirst preferred embodiment by a process which comprises a preliminarystep which involves separately storing, on the one hand, a composition(A) comprising, in a medium which is suitable for dyeing, at least onedeveloper compound, especially selected from para-phenylenediamines andbis(phenyl)alkylenediamines, and the acid-addition salts thereof, atleast one coupler, especially selected from meta-phenylenediamines andthe acid-addition salts thereof, and at least one cationic direct dye,on the other hand, a composition (B) containing, in a medium which issuitable for dyeing, at least one oxidizing agent and mixing themtogether at the time of use before applying this mixture to the keratinfibers.

According to a second preferred embodiment for the preparation of theready-to-use dye composition, the process includes a preliminary stepwhich involves separately storing, on the one hand, a composition (A)comprising, in a medium which is suitable for dyeing, at least onedeveloper compound, especially selected from para-phenylenediamines andbis(phenyl)alkylenediamines, and the acid-addition salts thereof, atleast one coupler compound, especially selected frommeta-phenylenediamines and the acid-addition salts thereof; on the otherhand, a composition (A′) comprising, in a medium which is suitable fordyeing, at least one cationic direct dye and, lastly, a composition (B)containing, in a medium which is suitable for dyeing, at least oneoxidizing agent as defined above, and mixing them together at the timeof use before applying this mixture to the keratin fibers.

The composition (A′) used according to this second variant of theprocess in accordance with the invention can optionally be in powderform, the cationic direct dye(s) in accordance with the invention itself(themselves) constituting, in this case, all of the said composition(A′) or optionally being dispersed in an organic and/or inorganicpulverulent excipient.

When it is present in the composition A′, the organic excipient can beof synthetic or plant origin and is selected in particular fromcrosslinked and non-crosslinked synthetic polymers, polysaccharides suchas celluloses and modified or unmodified starches, as well as naturalproducts containing them such as sawdust and plant gums (guar gum, carobgum, xanthan gum, etc.).

When it is present in the composition (A′), the inorganic excipient cancontain metal oxides such as titanium oxides, aluminium oxides, kaolin,talc, silicates, mica and silicas.

An very suitable excipient in the colouring compositions for carryingout the method according to the invention is sawdust.

The powdered composition (A′) can also contain binders or coatingproducts in an amount which preferably does not exceed approximately 3%by weight relative to the total weight of the said composition (A′).

These binders are preferably selected from oils and liquid fattysubstances of inorganic, synthetic, animal or plant origin.

The composition (A′) may optionally also contain other adjuvants, inpowdered form, in particular surfactants of any kind, hair conditionerssuch as, for example, cationic polymers, etc.

Another subject of the invention is a multi-compartment dyeing device or“kit” or any other multi-compartment packaging system, as described forexample in U.S. Pat. No. 6,228,129, especially in column 26, lines 13 to24, especially in column 26, line 26 to column 27, line 9, or. A firstcompartment which contains the composition (A) as defined above, anoptional second compartment contains the composition (A) as definedabove, when it is present, and a third compartment contains theoxidizing composition (B) as defined above. These devices can beequipped with means which allow the desired mixture to be applied to thehair, such as the devices described in French patent FR-2,586,913, thedisclosure of which is specifically incorporated by reference herein.

An oxidizing agent, which may be added to the colouring compositions forcarrying out the method according to the invention containingcomposition, comprises an oxidizing agent and a base.

Further, this composition comprises for this oxidizing agent containingcomposition customary adjuvant and additives.

The formulations are for example a solution, especially a thickenedwatery or watery alcoholic solution, a cream, foam, a gel, a powder oran emulsion.

In general, preference is given to a cream formulation, a gelformulation or a foam formulation, and especially a foam formulation.

But, if stability- or solubility-problems arise it may of advantage touse powder formulation as for example described in DE 197 13 698, page2, line 26 to 54 and page 3, line 51 to page 4, line 25, and page 4,line 41 to page 5 line 59.

The oxidizing agent (calculated as hydrogen peroxide) is present in thiscomposition in 0.5 to 12% by weight, in particular from 1 to 6% byweight based on the totals weight of the oxidizing agent containingcomposition.

The pH-value of the oxidizing agent containing composition is usuallyabout 2 to 7, and in particular about 3 to 6.

An oxidizing agent free composition, which may be added to the colouringcompositions for carrying out the method according to the invention,comprises a developer compound and a coupler compound and a reductionagent, or a developer compound or/and optionally a reduction agent, or acoupler compound and a reduction agent.

Further, an oxidizing agent free composition may additionally comprise adirect dye as for example described in German Patent Application 199 59479, column 3, line 12 to line 16.

Additionally, the oxidizing agent free composition usually comprisescustomary adjuvant and additives. Preferred are those, which aredescribed in German Patent Application, in column 3, line 17 to line 41.

The pH-value of the oxidizing agent free composition is usually about 3to 11, and in particular about 5 to 10, and most particular about 9 to10.

For adjusting the pH-value organic or inorganic acids, as for exampledescribed in German Patent Application 199 59 479, column 3, line 46 toline 53 are suitable.

The colouring compositions for carrying out the method according to theinvention may also be combined with hair dye compositions comprising anacid dye. Hair dye compositions comprising an acid dye are known. Forexample, they are described in “Dermatology”, edited by Ch. Culnan, H.Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch.Zviak, The Science of Hair Care, chapter 7, pages 248-250, especially onpage 253 and 254.

The hair dye compositions comprising an acid dye have a pH of 2-6,preferably 2-5, more preferably 2.5-4.0. If the pH is too low, theresulting composition may roughen the hair, scalp and hand skin due toan acid component in some cases. If the pH is too high, the penetrationaccelerating effect on the acid dye is lowered.

The colouring method according to the present invention may also readilybe used in combination with other dyes and/or adjuvants used in thecolouring of hair, for example

-   -   acid dye and an alkylene carbonate, as described in U.S. Pat.        No. 6,248,314, especially in examples 1 and 2, or    -   acid hair dye compositions comprise various kinds of organic        solvents represented by benzyl alcohol as a penetrant solvent        have good penetrability into hair, as described in Japanese        Patent Application Laid-Open Nos. 210023/1986 and 101841/1995,        or    -   acid hair dye compositions with a water-soluble polymer or the        like to prevent the drooping of the hair dye composition, as        described for example in Japanese Patent Application Laid-Open        Nos. 87450/1998, 255540/1997 and 245348/1996, or    -   acid hair dye compositions with a water-soluble polymer of        aromatic alcohols, lower alkylene carbonates, or the like as        described in Japanese Patent Application Laid-Open No.        53970/1998 and Japanese Patent Publication No. 23911/1973.

Preferred keratin fibers are human hair.

The dyes or dye precursors are suitable for all-over colouring of thehair, that is to say when colouring the hair on a first occasion, andalso for re-colouring subsequently, or colouration of locks or parts ofthe hair.

The dyes or dye precursors are applied to hair for example throughmassage in by hand, a comb, a brush, or a bottle, or a bottle, which iscombined with a comb or a nozzle.

In general, the dyes or dye precursors are applied to the hair in aformulation with further components, like adjuvants or additional dyesor dye precursors.

After the application of the dyeing composition the dyed hair iscustomary rinsed. Customary, the rinsing is conducted with water.

In a suitable embodiment of the processes of the present invention fordyeing human hair, the dyeing composition is not rinsed off, but washedoff with a commercially available hair shampoo.

In general, the dyed hair is dried after rinsing and/or washing.

Customary, drying is conducted with hot air by means of a drier or thelike, since color migration to clothes and the like becomes scarcelycaused.

In the context of the present invention, the expression “a further dye”,denotes preferably an oxidation dye, a diazotised compound, a cappeddiazotised compound and/or coupler compound, or acid dye, especiallyselected a cationic, anionic or uncharged direct dye.

A very suitable process for dyeing keratin fibers comprise contactingthe keratin fibers under alkaline conditions with at least one cappeddiazotized compound and a coupler compound, with the proviso that the pHis adjusted in the range from 2 to 6 in the last process step.

Adjusting the pH is achieved in conventional manner by adding an acid asdescribed for example in EP 962218, especially on page 3, lines 12 to16.

Acids are for example tartaric acid or citric acid, a citric acid gel, asuitable buffer solution with optionally an acid dye.

Preferred technical forms of acids are a solution, a gel, a cream, afoam, a conditioner, a emulsion, a shampoo and more preferred a shampooor a conditioner.

In the context of the present invention, the expression “alkalinecondition”, denotes to all process steps without those wherein acidconditions are explicitly described.

All processes for dyeing keratin fibers, in particular human hair,usually comprise after contacting the keratin fiber with a dye and/oroptionally or an oxidizing agent

-   -   a) leaving the fibers to stand, and    -   b) then rinsing the fibers.

The process for dyeing keratin fibers, in particular human hair, withdirect dyes comprises

-   -   a) contacting the keratin fibers with a direct dye.

The process for dyeing is for example described in WO 01/66646 on page15, line 32 to page 16, line 2.

Usually, the dyeing compositions are usually applied to the hair in anamount of from 50 to 100 g.

This composition is left on the fiber at 15 to 45° C. for 5 to 30minutes, and in particular for 10 to 20 minutes at 20 to 30° C.

The method of colouring according to the invention in combination withat least one direct dye may further concerns a process for dyeingkeratin fibres comprises

-   -   a) contacting the keratin fibers with at least one direct dye, a        base and an oxidizing agent.

Compositions comprising at least one direct dye and an oxidizing agent,are for example described in WO 97/20545, on page 3, line 24 to page 11,line 4, and especially on page 4, line 9 to 17.

The composition comprising at least one direct dye, a base and anoxidizing agent is prepared by mixing at least one direct dye and abase, and then just before the dyeing of the hair, adding an oxidizingagent.

Alternatively, the oxidizing agent can be applied simultaneously with acomposition comprising at least one dye and a base.

Preferably, the process for dyeing keratin fibres with at least ondirect dye comprises using a multi-compartment dyeing device or ‘kits’as described for example in WO 97/20545, especially on page 4, line 19to line 27.

Suitable processes for enlightening dyeing, which can be used incombination with the method for colouring according to the invention aredescribed in WO 97/20545, on page 11 to page 13.

Suitable processes for dyeing with cationic dyes, which can be combinedwith the method of colouring according to the present invention, aredescribed

-   -   in WO 95/01772, especially on page 10, line 24 to page 11, line        16, and especially on page 11, line 29 to page 28, or    -   in WO 01/66646, especially on page 1, line 18 to page 3, line        16, and preferred from page 16, line 20 to page 22, or    -   in EP 970 685, especially on page 50, lines 15 to 43, and        preferred from page 50, line 46 to page 51, line 40, or    -   in DE-A-19 713 698, especially page 5, lines 26 to 60, or    -   a process of dyeing with direct dyes and oxidizing agent is        described in WO 97/20545, especially on page 10, line 10 to page        11, line 55 and preferably on page 11, line 6 to page 13, line        19.

Suitable processes for dyeing with combinations of cationic dyes andother dyes, which can be combined with the method of colouring accordingto the present invention, are:

-   -   mixtures of at least two cationic dyes as described in WO        95/01772, especially on page 11, lines 1 to 15, or    -   combinations of Pyrazolo-[1,5-a]-pyrimidines with at least one        cationic dye as described in EP 998,908, especially on page 50,        lines 15 to 28, or    -   combinations of cationic dyes as described in FR-2788432,        especially on page 49, line 28 to page 52, and preferred on page        50, lines 16 to 28, or    -   combinations of direct dyes and/or an oxidation dye and        oxidizing agents in the form of permanent-wave fixing solution,        especially with direct dyes as described in DE-A-19 713 698,        especially on page 2, lines 12 to 23, especially on page 4, line        65 to page 5, line 59, or    -   combinations of cationic dyes and an oxidation dye of the        developer compound type and oxidizing agents as described in EP        850 638, especially on page 29, line 42 to page 30, line 20 and        preferred on page 30, line 25 to page 32, line 30, or    -   combinations of an extemporaneous mixture of a composition (A)        containing one or more oxidation dye precursors and optionally        one or more couplers, and of a composition (B), in powder form,        containing one or more direct dye, preferably cationic,        optionally dispersed in an organic pulverulent excipient and/or        a mineral pulverulent excipient, and a composition (C)        containing one or more oxidizing agent as described in U.S. Pat.        No. 6,190,421, especially in column 8, lines 43 to 52, and        preferably in column 8, line 55 to column 9, line 55, or    -   a ready-to-use composition comprising, at least one oxidation        base, at least one cationic direct dye and at least one enzyme        of 2-electron oxidoreductase type in the presence of at least        one donor for the said enzyme as described in U.S. Pat. No.        6,228,129, especially in column 25, line 56 to column 27, line        9, or    -   a ready-to-use composition or multi-compartment dyeing device        comprising compositions of at least one direct cationic dye and        at least one nitrated benzene dye as described in WO 99/20235 on        page 34, line 27 to page 37, or    -   a ready-to-use composition or multi-compartment dyeing device        comprising compositions of at least one direct cationic dye and        at least one autooxidisable oxidation dye, especially benzene,        indol and indoline derivatives as described in WO 99/20234,        especially on page 32, line 20 to page 35, oxidation dyeing        compositions of at least one direct dye and at least one        meta-Aminophenol derivative and at least one developer compound        and an oxidizing agent as described in EP 850 636, especially on        page 18, line 1 to page 22, line 11, or    -   oxidation dyeing compositions of at least one direct dye and at        least one developer compound selected from the group of        para-Phenylenediamine derivatives and Bis-Phenylalkylenediamine        and, and at least one coupler compound selected from the group        of meta-Diphenols and an oxidizing agent, as described in        EP-A-850 637, especially on page 19, line 24 to page 22, line        57,    -   cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives,        as described in EP 998 908, especially on page 47, line 25 to        page 50, line 29, or    -   arianors and/or oxidative dyes, as described in FR-2 788 432,        especially on page 2, line 16 to page 3, line 16, and page 5,        line 19 to page 14, line 8, and combinations with cationic dyes        as described on page 14, line 23 and following, or    -   oxidative dye precursors (unsaturated aldehyde and coupler        compounds), as described in German Patent Application 197 172        24, especially on page 3, line 36 to page 9 line 64.

The method of colouring of keratin fibers, especially human hair,according to the present invention may combined with direct dyes andoxidative dyes.

The process for dyeing keratin fibers with direct dyes and oxidativedyes, in particular human hair, comprises

-   -   a) contacting the keratin fibers with an oxidizing agent,        optionally containing at least a direct dye,    -   b) then contacting the keratin fibers with an oxidizing agent        free composition, optionally containing at least a direct dye,        or    -   a) contacting the keratin fibers with an oxidizing agent free        composition, optionally containing at least a direct dye,    -   b) then contacting the keratin fibers with an oxidizing agent,        optionally containing at least a direct dye.

The method of colouring according to the present invention may combinedwith a process for dyeing keratin fibers with direct dyes and oxidativedyes, which comprises

-   -   a) contacting the keratin fibers with at least one direct dye,    -   b) then contacting the keratin fibers with an oxidizing agent        free composition.

Such process is for example described in DE 199 41 450, especially onpage 5, lines 50 to 58, and on page 8, line 31 to 46.

Oxidizing agent is usually applied in form of an oxidizing agentcontaining composition. Oxidizing agent free composition containing atleast one coupler compound, at least one developer compound, a base anda reduction agent.

Customary, the oxidizing agent containing composition is evenly appliedin a sufficient amount related to the amount of hair, usually with 30 to200 g.

In general, the oxidizing agent containing composition is left on thefiber at 15 to 45° C. for 0 to 15 minutes, and in particular for 0 to 5minutes.

Then the oxidizing agent free composition is applied to the hair.

In general, the direct dye and oxidizing agent free composition is lefton the fiber at 15 to 50° C. for 5 to 45 minutes, and in particular for10 to 25 minutes.

The coupler and developer compounds of the oxidizing agent freecomposition can be applied simultaneously or in succession. Preferred isa simultaneous application.

One preferred embodiment of the process is to wash the hair with shampooand or a weak acid, such as citric acid or tartrate acid.

The direct dyes, which are stable to reduction can stored together withthe oxidizing agent free compositions and are applicable as composition.

It is of advantage to prepare compositions of direct dyes, which are notstable to reduction, with oxidizing agent free compositions just beforethe dyeing process.

Further, a direct dye and an oxidizing agent free composition can beapplied simultaneously or in succession.

A suitable process for the coloration of keratin fiber with direct dyesand oxidation dyes, which can be used in combination with the method ofcolouring according to the present invention, comprises

-   -   a) mixing at least one direct dye and optionally at least one        coupler compound and at least one developer compound, and an        oxidizing agent, which optionally contains at least one direct        dye, and    -   b) then contacting the keratin fibers with the mixture as        prepared in step a).

A further suitable process for the coloration of keratin fiber withdirect dyes and oxidation dyes, which can be used in combination withthe method of colouring according to the present invention, comprises

-   -   a) mixing at least one autooxidable compound and at least one        developer compound and at least one direct dye, and    -   b) then contacting the keratin fibers with the mixture prepared        in step a).

The direct dye is usually applied in form of a composition, comprisingfurther adjuvants, in particular an aqueous composition.

In general the mixing is conducted just before contacting the keratinfibers. Usually, the mixture prepared in process step a) is evenlyapplied in a sufficient amount related to the amount of hair, usuallywith 30 to 200 g. In general, the mixture is left on the fiber at 15 to45° C. for 0 to 50 minutes, and in particular for 30 to 45 minutes.

One preferred embodiment of the processes is to wash the hair withshampoo and or a weak acid, such as citric acid or tartrate acid, as forexample described in EP 962218, especially on page 3, lines 9 to 18.

One suitable embodiment of the present invention concerns in addition tothe method according to the present invention, the separate applicationof a direct dye an oxidation dye is for example as described in DE-A-19713 698, especially page 4, line 65 to page 35, line 59, wherein thekeratin fibres are contacted in a first step with a direct dye,especially in form of a tinting powder, and an oxidizing agent, andthen, in a second step, with an oxidizing free composition, especiallyin form of a powder.

Further, it is possible to apply a for example a ready-to-usecomposition for the oxidation dyeing of keratin fibers, in particularhuman keratin fibers such as hair, as described in U.S. Pat. No.6,190,421, in column 1, line 65 to column 3, line 65, especially incolumn 10, line 62 to column 12, line 65.

According to this process, the ready-to-use dye composition as definedabove is applied to the fibers and is left on them for an exposure timepreferably of from approximately 3 to approximately 40 minutes, morepreferably from approximately 5 to approximately 30 minutes, after whichthe fibers are rinsed, optionally washed with shampoo, rinsed again anddried.

If unsaturated aldehydes are used as oxidative precursor dye togetherwith a coupler compound no oxidizing agent is needed as described inGerman Patent Application 19 717 224.5. Nevertheless, it may bedesirable to conduct the colouring in the presence of oxidizing agents,if lightening or a unified colouration of the keratin fiber isenvisaged.

The process of dyeing keratin fibers with oxidative dye precursors,which can be used in combination with the method of colouring accordingto the present invention, comprises

-   -   a) contacting the keratin fibers with an unsaturated aldehyde, a        coupler compound and a direct dye.

In all above-cited dyeing processes it is also possible to apply amixture of coupler compounds/and or developer compounds and/differentdirect dyes.

Another preferred embodiment of the processes for oxidative dyeing ofkeratin fibers, which can be used in combination with the method ofcolouring according to the present invention, comprise applying to thekeratin fibers after contacting with an oxidizing agent free compositioncontaining a coupler compound and a developer compound and optionally adirect dye with a further oxidizing agent free composition containing acoupler compound and a developer compound and optionally an oxidizingagent containing composition and optionally a direct dye by a pH rangefrom 5 to 7, preferred from 6.5 to 7. In general the keratin fiber isnot washed or rinsed afterwards as for example described in EP 962217,especially on page 3, lines 9 to 17.

The developer and coupler compounds can be applied separately,simultaneously or in succession.

In all above-cited dyeing processes with oxidation dye precursors it isalso possible to apply a mixture of coupler compounds/and or developercompounds.

A more suitable process for the dyeing of keratin fibers with oxidativedyes, which can be used in combination with the method of colouringaccording to the present invention, comprises,

-   -   a) contacting the keratin fibers with an oxidizing agent        containing composition,    -   b) then contacting the keratin fibers with an oxidizing agent        free composition.

Such process is for example described in DE 19959479, especially incolumn 3, line 54 to column 4, line 8.

Usually, the oxidizing agent containing composition is evenly applied ina sufficient amount related to the amount of hair, usually with 30 to200 g.

In general, the oxidizing agent containing composition is left on thefiber at 15 to 50° C. for 0 to 15 minutes, and in particular for 0 to 30minutes.

Then the oxidizing agent free composition is applied.

Customary, the oxidizing agent free composition is left on the fiber at15 to 50° C. for 5 to 45 minutes, and in particular for 10 to 25minutes.

The coupler and developer compounds of oxidizing agent free compositionscan be applied as an admixture, or separately simultaneously or insuccession. Preferred is the application of an admixture.

One suitable embodiment of the processes is to wash the hair withshampoo and or a weak acid, such as citric acid or tartrate acid, as forexample described in EP 962218, especially on page 3, lines 9 to 18.

A further suitable process for the coloration of keratin fiber withoxidation dyes, which can be used in combination with the method ofcolouring according to the present invention, comprises

-   -   a) mixing at least one coupler compound and developer compound,        and an oxidizing agent, and    -   b) then contacting the keratin fibers with the mixture as        prepared in step a).

A further suitable process for the coloration of keratin fiber with anoxidation dye, which can be used in combination with the method ofcolouring according to the present invention, comprises

-   -   a) mixing an autooxidable compound and a developer compound, and    -   b) then contacting the keratin fibers with the mixture prepared        in step a).

Especially preferred is a process for dyeing keratin fibers, inparticular human hair, with capped diazotised compounds, whichcomprises,

-   -   a) contacting the keratin fibers, under alkaline conditions,        with at least one capped diazotised compound and a coupler        compound, and optionally an oxidising agent, and optionally in        the presence of a further dye,    -   b) then adjusting the pH in the range of 6 to 2 by treatment        with acid, optionally in the presence of a further dye.

The capped diazotised compound and coupler compound and optionally theoxidizing agent, can be applied in any desired order successively, orsimultaneously.

Preferably, however, the capped diazotised compound and the couplercompound are applied simultaneously, in a single composition.

Customary the dyeing composition is applied to the hair in an amount offrom 50 to 100 g.

In the context of the present invention, the expression “alkalineconditions” denotes a pH in the range from 8 to 10, preferably 9-10,especially 9.5-10.

Adding bases, for example sodium carbonate, ammonia or sodium hydroxide,to the hair or to the dye precursors, the capped diazotised compoundand/or the water-soluble coupling component, or to colouringcompositions comprising the dye precursors, customarily achieve thealkaline conditions.

In the second stage, the diazotised compound and the coupler compoundare then caused to react, preferably by lowering the pH to a value offrom 6 to 2, especially from 3 to 4.

A preferred embodiment of all processes of the present invention fordyeing keratin fibers comprise contacting the keratin fibers underalkaline conditions with at least one capped diazotized compound and acoupler compound, with the proviso that the pH is adjusted in the rangefrom 2 to 6 in the last process step.

Adjusting the pH is achieved in conventional manner by adding an acid asdescribed for example in EP 962218, especially on page 3, lines 12 to16.

Acids are for example tartaric acid or citric acid, a citric acid gel, asuitable buffer solution with optionally an acid dye.

Preferred technical forms of acids are a solution, a gel, a cream, afoam, a conditioner, a emulsion, a shampoo and more preferred a shampooor a conditioner.

The ratio of the amount of alkaline colouring composition applied in thefirst stage to that of acid colouring composition applied in the secondstage is preferably about from 1:3 to 3:1, especially about 1:1.

This first alkaline and then acid dyeing compositions each are left onthe fiber at 15 to 45° C. for 5 to 60 minutes, and in particular for 5to 45 minutes at 20 to 30° C.

In the methods according to the invention, whether or not colouring isto be carried out in the presence of a further dye will depend upon thecolour shade to be obtained. In the context of the present invention,the expression “a further dye”, denotes preferably an oxidation dye, adiazotised compound, a capped diazotised compound and/or couplercompound, or acid dye, especially selected a cationic, anionic oruncharged direct dye, especially a cationic dye selected from the groupof the cationic dyes as described in WO 95/01772, especially on page 2,line 7 to page 4, line 1, and preferred on page 4, line 35 to page 8,line 21 with the given preferences, and as described in WO 01/66646,especially on page 1, line 18 to page 3, line 16, or a mixture of atleast two cationic dyes as described in WO 95/01772, especially on page8, line 34 to page 10, line 22.

A preferred embodiment of the process for dyeing keratin fibres withcapped diazotised compounds and a coupler compound, comprises contactingthe keratin fibres with more than one capped diazotised compound and/ormore than one coupler compound.

Preferred is a process of the present invention for the coloration ofkeratin fiber with capped diazotised compounds comprises

-   -   a) mixing, under alkaline conditions, at least one with capped        diazotised compound and at least one coupler compound and at        least one direct dye and optionally at least one developer        compound; and an oxidizing agent, which optionally contains at        least one direct dye, and    -   b) then contacting the keratin fibers with the mixture as        prepared in step a),    -   c) then adjusting the pH in the range of 6 to 2 by treatment        with acid, optionally in the presence of a further dye.

More preferred is a process for dyeing keratin fibres with at least onecapped diazotized compound, which comprises

-   -   a) mixing under alkaline conditions, at least one capped        diazotized compound and at least one direct dye, a base and an        oxidizing agent, and    -   b) then contacting the keratin fibers with the mixture as        prepared in step a),    -   c) then adjusting the pH in the range of 6 to 2 by treatment        with acid, optionally in the presence of a further dye.

Further, preferred is a process for the coloration of keratin fiber withcapped diazotised compounds comprising

-   -   a) mixing under alkaline conditions, at least one with capped        diazotised compound and at least one coupler compound and        optionally at least one direct dye and optionally at least one        developer compound, and optionally at least one autooxidable        compound, and    -   b) then contacting the keratin fibers with the mixture prepared        in step a),    -   c) then adjusting the pH in the range of 6 to 2 by treatment        with acid, optionally in the presence of a further dye.

A further suitable process for the two-step direct dyeing of keratinfibres, which can be used in combination with the method of colouringaccording to the present invention, is characterized in that,

-   -   a) contacting the keratin fibers with an oxidizing agent or an        oxidizing agent containing composition,    -   b) then contacting the keratin fibers with at least one capped        diazotised compound and at least a coupler compound and        optionally a direct dye or/and optionally an oxidizing agent        free composition,    -   c) then adjusting the pH in the range of 6 to 2 by treatment        with acid, optionally in the presence of a further dye.        or    -   a) contacting the keratin fibers with at least one capped        diazotised compound and a coupler compound and optionally a        direct dye or/and optionally an oxidizing agent free        composition,    -   b) then contacting the keratin fibers with an oxidizing agent or        an oxidizing agent containing composition,    -   c) then adjusting the pH in the range of 5 to 2 by treatment        with acid, optionally in the presence of a further dye.        d)

The present invention also concerns a process for the colouration ofkeratin fibers, especially human hair, with acid dyes, which can be usedin combination with the method of colouring according to the presentinvention.

The process comprises additionally

-   -   a) contacting the keratin fiber with an acid dye.

Customary, the dyeing composition comprising an acid dye is applied tothe hair in an amount of from 50 to 100 g.

This in a composition is left on the fiber at 15 to 45° C. for 1 to 30minutes, and in particular for 0 to 15 minutes at 20 to 30° C.

Preferably the hair is rinsed and than washed with shampoo and morepreferably not rinsed, but washed with shampoo.

The shampoo used herein includes a shampoo comprising 5-20% of a usualanionic surfactant such as an alkylsulfate or polyoxyethylenealkylsulfate.

The invention relates also to colouring compositions for carrying outthe method according to the invention, which compositions comprise

-   -   a) at least one compound of formula (1), (2) and/or (3)        indicated hereinbefore,    -   b) a medium for adjusting the pH,    -   c) water, and, optionally,    -   d) further additives.

Further, the invention relates also to colouring compositions forcarrying out the method according to the invention, which compositionscomprise

-   -   a) at least one compound of formula (1), (2) and/or (3)        indicated hereinbefore,    -   b) a medium for adjusting the pH,    -   c) water,    -   d) at least one coupling component, and, optionally,    -   e) further additives,        with the provisos that

-   (i) if the water-soluble coupling component is    then the capped diazonium compound must not be    and

-   (ii) if the water-soluble coupling component is    then the capped diazonium compound must not be

Further, the invention relates also to colouring compositions forcarrying out the method according to the invention, which compositionscomprise

-   a) at least one compound of formula (1), (2) and/or (3) indicated    hereinbefore,-   b) a medium for adjusting the pH,-   c) water,-   d) at least one water-soluble coupling component selected from the    group consisting of acylacetarylamides, phenols, naphthols,    pyridones, quinolones, pyrazoles, indoles, diphenylamines, anilines,    aminopyridines, pyrimidones, naphthylamines, aminothiazoles,    thiophenes or hydroxypyridines, which all may carry further    substituents, for example amino, alkylamino, dialkylamino, halogen,    alkyl, alkoxy, aryl, especially phenyl or naphthyl, or aryloxy, but    especially a group imparting water solubility, e.g. hydroxy, carboxy    or sulfo, and, optionally,-   e) further additives,    with the provisos that-   (i) if the water-soluble coupling component is    then the capped diazonium compound must not be    and-   (ii) K the water-soluble coupling component is    then the capped diazonium compound must not be

Especially preferred compositions comprise

-   a) at least one compound of formula (1), (2) and/or (3) indicated    hereinbefore,-   b) a medium for adjusting the pH,-   c) water,-   d) at least one water-soluble coupling component selected from the    group consisting of acylacetarylamides, phenols, naphthols,    pyridones, quinolones, pyrazoles, indoles, diphenylamines, anilines,    aminopyridines, pyrimidones, naphthylamines, aminothiazoles,    thiophenes or hydroxypyridines, which all may carry further    substituents, for example amino, alkylamino, dialkylamino, halogen,    alkyl, alkoxy, aryl, especially phenyl or naphthyl, or aryloxy, but    especially a group imparting water solubility, e.g. hydroxy, carboxy    or sulfo,-   e) a further dye, preferably an oxidation dye, or a cationic,    anionic or uncharged direct dye, especially a cationic dye selected    from the group of the cationic dyes as described in WO 95/01772 and    WO 01/66646, and, optionally,-   f) further additives,    with the provisos that-   (i) if the water-soluble coupling component is    then the capped diazonium compound must not be    and-   (ii) if the water-soluble coupling component is    then the capped diazonium compound must not be

The colouring compositions used in accordance with the invention and theoptionally used oxidation dye precursors may be stored either separatelyor together, either in a liquid to paste-like preparation (aqueous ornon-aqueous) or in the form of a dry powder. When the components arestored together in a liquid preparation, the preparation should besubstantially anhydrous in order to reduce reaction of the components.When they are stored separately, the reactive components are intimatelymixed with one another only immediately before use. In the case of drystorage, before use a defined amount of hot (from 50 to 80° C.) water isusually added and a homogeneous mixture prepared.

The following Examples serve to illustrate the invention withoutlimiting the invention thereto. Unless specified otherwise, parts andpercentages relate to weight. The amounts of dye specified are relativeto the material being coloured.

EXAMPLE 1

A) Preparation of Triazenes

43.4 g of 4-chloro-2-amino-1-methylbenzene are mixed with 81 g of 32%hydrochloric acid and cooled to 0° C. Then, over the course of one hour,75 ml of 4N aqueous sodium nitrite solution are added dropwise, withstirring, the temperature being maintained at from 0 to 5° C. Theresulting solution is then added dropwise, over the course of 15minutes, to an aqueous solution of 30 g of sarcosine and 90 g of sodiumcarbonate in 250 ml of water at a temperature of 0-5° C. The resultingbrown suspension is filtered, the residue is recrystallised from ethanoland dried in air. 66.2 g of3-methyl-1-(5-chloro-2-methylphenyl)-3-(carboxylmethyl)triazene areobtained in the form of brownish-yellow powder. (Yield: 91%). Thecompound has the following formula and its ¹H-NMR spectrum exhibits thechemical shifts indicated.

EXAMPLES 2 to 4

Using a procedure analogous to that described in Example 1, thefollowing compounds are prepared Example 2 3 4

Colouring Method A:

A strand of bleached human hair is immersed, for 30 minutes at roomtemperature, in an aqueous solution containing 0.2M triazene and 0.2Mcoupling component, which has been adjusted to pH 10.0 using sodiumcarbonate, ammonia or NaOH. The strand is removed, excess solution iswiped off and the strand is immersed for 5 minutes in a pH 3 buffersolution containing 4% sodium citrate and 2% citric acid. The strand isthen thoroughly rinsed using water and, where appropriate, a shampoosolution and is dried. Hair coloured in the shades mentioned isobtained, with outstanding fastness properties, especially fastness towashing properties.

Colouring Method B:

A strand of bleached human hair is immersed, for 30 minutes at roomtemperature, in an aqueous solution that contains 0.2M triazene, 0.2Mcoupling component and 0.2M of hydrogen peroxide (6%) and that has beenadjusted to a pH in the range pH 9.8-10 using sodium carbonate, ammoniaor NaOH. After contact for 5-30 minutes, there is applied to the strand,without its being rinsed, an amount, corresponding to the weight oftriazene and coupling component originally used, of a mixture comprising12.5% strength aqueous citric acid gel, which contains 0.1% by weight ofa cationic dye selected from the group of the cationic dyes as disclosedin WO 95/01772 and in WO 01/66646. The strand is then combed throughthoroughly, a pH of about 7 being obtained. After contact for 15minutes, the treated strand is treated again with the above mixturecomprising 12.5% strength citric acid gel and 0.1% by weight of acationic dye selected from the group of the cationic dyes as disclosedin WO 95/01772 and in WO 01/66646 at pH 4 for 5 minutes, rinsedthoroughly with water and then dried. Hair is obtained with outstandingfastness properties, especially fastness to washing and fastness toshampooing properties.

Colouring Method C:

A strand of bleached human hair is immersed, for 30 minutes at roomtemperature, in an aqueous solution that contains 0.2M triazene, 0.2Mcoupling component and 0.2 mol of hydrogen peroxide (6%) and that hasbeen adjusted to a pH in the range pH 9.8-10 using sodium carbonate,ammonia or NaOH. After contact for 5-30 minutes, there is applied to thehair, without its being rinsed, an amount, corresponding to the weightof triazene and coupling component originally used, of a 12.5% strengthaqueous citric acid gel containing 0.1% by weight of a cationic dyeselected from the group of the cationic dyes as disclosed in WO 95/01772and in WO 01/66646 and 4% sodium citrate; the hair is combed throughthoroughly, a pH of about 3 being obtained. Then, after a contact timeof 5-30 minutes, the hair is rinsed thoroughly with water and dried.Hair is obtained with outstanding fastness properties, especially goodfastening to washing properties.

Colouring Method D:

A strand of bleached human hair is immersed, for 30 minutes at roomtemperature, in an aqueous solution containing 0.2M triazene, 0.2Mcoupling component, 0.2 mol of hydrogen peroxide (6%) and from 0.1 to 1%by weight, based on the weight of the triazene and coupling component,of a cationic dye selected from the group of the cationic dyes asdescribed in WO 95/01772 and in WO 01/66646. The strand is then adjustedto a pH in the range pH 9.8-10 using sodium carbonate, ammonia or NaOH.After contact for 5-30 minutes, there is applied to the hair, withoutits being rinsed, an amount, corresponding to the weight of triazene andcoupling component originally used, of a 12.5% strength aqueous citricacid gel and 4% sodium citrate and the hair is combed throughthoroughly, a pH of about 3 being obtained. Then, after a contact timeof 5-30 minutes, the hair is rinsed thoroughly with water and dried.Hair is obtained with outstanding fastness properties, especially goodfastness to washing properties. Triazene Coupler Hair colour Example 5:

carmine-red Example 6:

cherry-red Example 7:

reddish orange Example 8:

purple Example 9:

violet Example 10:

burgundy-red Example 11:

ruby-red Example 12:

yellow-ochre Example 13:

chestnut-brown Example 14:

copper-red Example 15:

brilliant orange Example 16:

greenish brown Example 17:

lemon-yellow Example 18:

reddish orange Example 19:

golden-yellow Example 20:

copper-red Example 21:

copper-red Example 22:

rust-red Example 23:

wine-red Example 24:

brown Example 25:

pink Example 26:

violet Example 27:

blue-black Example 28:

copper-red Example 29:

copper-coloured Example 30:

purple Example 31:

blue Example 32:

blue Example 33:

violet Example 34:

red Example 35:

vivid yellow Example 36:

scarlet Example 37:

copper-red Example 38:

vivid red Example 39:

brownish violet Example 40:

carmine-red Example 41:

dark-brown Example 42:

brownish orange Example 43:

vivid red Example 44:

vivid yellow Example 45:

orange Example 46:

reddish orange Example 47:

lemon-yellow Example 48:

straw-yellow Example 49:

brownish orange Example 50:

dull orange Example 51:

reddish orange Example 52:

red Example 53:

red Example 54:

cherry-red Example 55:

purplish black Example 56:

vivid yellow Example 57:

dull yellow Example 58:

greenish brown Example 59:

orange Example 60:

ruby-red Example 61:

pure red Example 62:

reddish purple Example 63:

violet Example 64:

reddish brown Example 65:

red Example 66:

red Example 67:

red Example 68:

cherry-red Example 69:

carmine-red

EXAMPLE 70

A strand of bleached human hair is coloured with 10 g of composition A.Composition A (pH = 10) Ingredients wt.-% cetyl stearyl alcohol 11.00oleth-5 5.0 oleic acid 2.5 stearic acid monoethanolamide 2.5 coconutfatty acid monoethanolamide 2.5 sodium lauryl sulfate 1.71,2-propanediol 1.0 ammonium chloride 0.5 EDTA, tetrasodium salt 0.2perfume 0.4 wheat protein hydrolysate 0.2 silica 0.1 triazene of Example52 (sodium salt) 6.88 coupler of Example 52 2.2 water ad 100

The mixture is allowed to act on the strand for 15 minutes at about 22°C. Then 10 g of a mixture of a 2% strength aqueous citric acid gelcontaining 4% sodium citrate, are applied to the strand and then combedthrough, whereupon a pH of about 3 is achieved. After contact for 30minutes, the strand is thoroughly rinsed and then dried.

A strong, intense, striking cherry red coloration having good fastnessto washing and fastness to rubbing properties is obtained.

EXAMPLE 71

A strand of medium blond human hair is treated with a mixture of equalparts by weight −5 g in each case—of 6% hydrogen peroxide solution andof composition B. Composition B (pH = 9.8) Ingredients wt.-% cetylstearyl alcohol 11.00 oleth-5 5.0 oleic acid 2.5 stearic acidmonoethanolamide 2.5 coconut fatty acid monoethanolamide 2.5 sodiumlauryl sulfate 1.7 1,2-propanediol 1.0 ammonium chloride 0.5 EDTA,tetrasodium salt 0.2 perfume 0.4 wheat protein hydrolysate 0.2 silica0.1 2,5-diaminotoluene sulfate 0.7 4-amino-2-hydroxytoluene 0.52,5,6-triamino-4-hydroxypyrimidine sulfate 0.2 sodium sulfite 1.0ascorbic acid 0.5 triazene of Example 52 (sodium salt) 13.76 coupler ofExample 52 4.4 Ammonia (25%) 9.2 water ad 100

After contact for 15 minutes at room temperature, about 22° C., 10 g ofa mixture of a 12.5% strength aqueous citric acid gel containing 0.1% byweight of a violet dye of the following formula

which is prepared analogously to WO 01/66646, Example 4, is applied tothe strand. The strand is then combed through, whereupon a pH of about 7is achieved. After contact for a further 15 minutes, the strand is againtreated with 10 g of the above mixture of citric acid gel and violetdye, whereupon a pH of about 4 is achieved. The mixture is allowed toact for 5 minutes at pH 4 and the strand is then washed with water andshampoo and then again with water. The strand is then dried.

A strong, intense, striking red violet coloration having good fastnessto washing and fastness to rubbing properties is obtained.

EXAMPLE 72

A strand of medium-blond human hair is coloured with a mixture of equalparts by weight −5 g in each case—of 6% hydrogen peroxide solution andof composition B according to Example 71.

The mixture is allowed to act on the strand for 20 minutes at roomtemperature, about 22° C. 10 g of a mixture of a 2% strength aqueouscitric acid gel containing 0.1% by weight of a violet dye according tothe above formula in Example 71, and 4% sodium citrate, are then appliedto the strand. The strand is then combed through, whereupon a pH ofabout 3 is achieved. After contact for 30 minutes, the strand isthoroughly rinsed and then dried.

A strong, intense, striking red violet coloration having good fastnessto washing and fastness to rubbing properties is obtained.

EXAMPLE 73

A strand of brown human hair is coloured with a mixture of equal partsby weight −5 g in each case—of 6% hydrogen peroxide solution and ofcomposition C. Composition C (pH = 9.8) Ingredients wt.-% cetyl stearylalcohol 11.00 oleth-5 5.0 oleic acid 2.5 stearic acid monoethanolamide2.5 coconut fatty acid monoethanolamide 2.5 sodium lauryl sulfate 1.71,2-propanediol 1.0 ammonium chloride 0.5 EDTA, tetrasodium salt 0.2perfume 0.4 wheat protein hydrolysate 0.2 silica 0.1 triazene of Example52 (sodium salt) 13.76 coupler of Example 52 4.4 water ad 100

The mixture is allowed to act on the strand for 30 minutes at about 22°C. 10 g of a mixture of a 2% strength aqueous citric acid gel containing0.1% by weight of a violet dye according to the above formula in Example71, and 4% sodium citrate, are then applied to the strand. The strand isthen combed through, whereupon a pH of about 3 is achieved. Aftercontact for 5 minutes, the strand is thoroughly rinsed and then dried.

A strong, intense, striking red violet coloration having good fastnessto washing and fastness to rubbing properties is obtained.

EXAMPLE 74

A strand of brown human hair is coloured with a mixture of equal partsby weight −5 g in each case—of 6% hydrogen peroxide solution and ofcomposition D. Composition D (pH = 9.8) Ingredients wt.-% cetyl stearylalcohol 11.00 oleth-5 5.0 oleic acid 2.5 stearic acid monoethanolamide2.5 coconut fatty acid monoethanolamide 2.5 sodium lauryl sulfate 1.71,2-propanediol 1.0 ammonium chloride 0.5 EDTA, tetrasodium salt 0.2perfume 0.4 wheat protein hydrolysate 0.2 silica 0.1 triazene of Example51 11.32 coupler of Example 51 (sodium salt) 4.2 coupler of example 522.2 water ad 100

The mixture is allowed to act on the strand for 30 minutes at about 22°C. 10 g of a mixture of a 2% strength aqueous citric acid gel containing0.1% by weight of a violet dye according to the above formula in Example71, and 4% sodium citrate, are then applied to the strand. The strand isthen combed through, whereupon a pH of about 3 is achieved. Aftercontact for 5 minutes, the strand is thoroughly rinsed and then dried.

A strong, intense, striking copper coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 75

A strand of brown human hair is coloured with a mixture of equal partsby weight −5 g in each case—of 6% hydrogen peroxide solution and ofcomposition E. Composition E (pH = 9.8) Ingredients wt.-% cetyl stearylalcohol 11.00 oleth-5 5.0 oleic acid 2.5 stearic acid monoethanolamide2.5 coconut fatty acid monoethanolamide 2.5 sodium lauryl sulfate 1.71,2-propanediol 1.0 ammonium chloride 0.5 EDTA, tetrasodium salt 0.2perfume 0.4 wheat protein hydrolysate 0.2 silica 0.1 coupler of Example52 4.4 triazene of Example 52 (sodium salt) 6.88 triazene of Example 43(sodium salt) 5.46 water ad 100

The mixture is allowed to act on the strand for 30 minutes at about 22°C. 10 g of a mixture of a 2% strength aqueous citric acid gel containing0.1% by weight of a violet dye according to the above formula in Example71, and 4% sodium citrate, are then applied to the strand. The strand isthen combed through, whereupon a pH of about 3 is achieved. Aftercontact for 5 minutes, the strand is thoroughly rinsed and then dried.

A strong, intense, bluish red coloration having good fastness to washingand fastness to rubbing properties is obtained.

EXAMPLE 76

A strand of blond undamaged human hair is coloured with a mixture ofequal parts by weight −5 g in each case—of 6% hydrogen peroxide solutionand of composition F. Composition F (pH = 9.8) Ingredients wt.-% cetylstearyl alcohol 11.00 oleth-5 5.0 oleic acid 2.5 stearic acidmonoethanolamide 2.5 coconut fatty acid monoethanolamide 2.5 sodiumlauryl sulfate 1.7 1,2-propanediol 1.0 ammonium chloride 0.5 EDTA,tetrasodium salt 0.2 perfume 0.4 wheat protein hydrolysate 0.2 silica0.1 Basic Red 51 0.2 triazene of Example 52 (sodium salt) 13.76 couplerof Example 52 4.4 water ad 100

-   A) The mixture is allowed to act on the strand for 30 minutes at    about 22° C. 10 g of a mixture of a 2% strength aqueous citric acid    gel containing 0.1% by weight of Basic Red 51 and 4% sodium citrate,    are then applied to the strand; the latter is then combed through,    whereupon a pH of about 3 is achieved. After contact for 5 minutes,    the strand is thoroughly rinsed and then dried.

A strong, intense, striking red coloration having good fastness towashing and fastness to rubbing properties is obtained.

-   B) The mixture is allowed to act on the strand for 30 minutes at    about 22° C. 10 g of a mixture of a 2% strength aqueous citric acid    gel containing 4% sodium citrate, are then applied to the strand;    the latter is then combed through, whereupon a pH of about 3 is    achieved. After contact for 5 minutes, the strand is thoroughly    rinsed and then dried.

A strong, intense, striking red coloration having good fastness towashing and fastness to rubbing properties is obtained.

-   C) The mixture is allowed to act on the strand for 30 minutes at    about 22° C. 10 g of a mixture of a 2% strength aqueous citric acid    gel containing 0.1% by weight of Basic Yellow 87 and 4% sodium    citrate, are then applied to the strand; the latter is then combed    through, whereupon a pH of about 3 is achieved. After contact for 5    minutes, the strand is thoroughly rinsed and then dried.

A strong, intense, striking copper red coloration having good fastnessto washing and fastness to rubbing properties is obtained.

EXAMPLE 77

A strand of bleached human hair is coloured with 10 g of composition G.Composition G (pH = 10) Ingredients wt.-% cetyl stearyl alcohol 11.00oleth-5 5.0 oleic acid 2.5 stearic acid monoethanolamide 2.5 coconutfatty acid monoethanolamide 2.5 sodium lauryl sulfate 1.71,2-propanediol 1.0 ammonium chloride 0.5 EDTA, tetrasodium salt 0.2perfume 0.4 wheat protein hydrolysate 0.2 silica 0.1 violet dye ofExample 71 0.2 triazene of Example 30 4.66 coupler of Example 30 3.16water ad 100

The mixture is allowed to act on the strand for 30 minutes at about 22°C. 10 g of a mixture of a 2% strength aqueous citric acid gel containing4% sodium citrate are then applied to the strand; the latter is thencombed through, whereupon a pH of about 3 is achieved. After contact for5 minutes, the strand is thoroughly rinsed and then dried.

A strong, intense, striking violet coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 78

A strand of bleached human hair is coloured with 10 g of composition H.Composition H (pH = 10) Ingredients wt.-% cetyl stearyl alcohol 11.00oleth-5 5.0 oleic acid 2.5 stearic acid monoethanolamide 2.5 coconutfatty acid monoethanolamide 2.5 sodium lauryl sulfate 1.71,2-propanediol 1.0 ammonium chloride 0.5 EDTA, tetrasodium salt 0.2perfume 0.4 wheat protein hydrolysate 0.2 silica 0.1 triazene of Example36 4.88 coupler of Example 36 4.79 water ad 100

The mixture is allowed to act on the strand for 15 minutes at about 22°C. Then 10 g of a mixture of a 2% strength aqueous citric acid gelcontaining 0.1% by weight of a red dye of the following formula

which can be prepared, for example, as described in WO 02/30374,according to Preparation Example 2, compound of formula 101, and 4%sodium citrate, are applied to the strand and then combed through,whereupon a pH of about 3 is achieved. After contact for 35 minutes, thestrand is thoroughly rinsed and then dried.

A strong, intense, striking scarlet coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 79

A strand of bleached human hair is coloured with 10 g of composition 1.Composition I (pH = 10) Ingredients wt.-% cetyl stearyl alcohol 11.00oleth-5 5.0 oleic acid 2.5 stearic acid monoethanolamide 2.5 coconutfatty acid monoethanolamide 2.5 sodium lauryl sulfate 1.71,2-propanediol 1.0 ammonium chloride 0.5 EDTA, tetrasodium salt 0.2perfume 0.4 wheat protein hydrolysate 0.2 silica 0.1 triazene of Example36 4.88 coupler of Example 36 4.79 Basic Orange 31 0.2 water ad 100

The mixture is allowed to act on the strand for 30 minutes at about 22°C. Then 10 g of a mixture of a 2% strength aqueous citric acid gelcontaining 4% sodium citrate, are applied to the strand and then combedthrough, whereupon a pH of about 3 is achieved. After contact for 5minutes, the strand is thoroughly rinsed and then dried. A strong,intense, striking scarlet coloration having good fastness to washing andfastness to rubbing properties is obtained.

EXAMPLE 80

A strand of blond undamaged human hair is coloured with 10 g ofcomposition J. Composition J (pH = 10) Ingredients wt.-% cetyl stearylalcohol 11.00 oleth-5 5.0 oleic acid 2.5 stearic acid monoethanolamide2.5 coconut fatty acid monoethanolamide 2.5 sodium lauryl sulfate 1.71,2-propanediol 1.0 ammonium chloride 0.5 EDTA, tetrasodium salt 0.2perfume 0.4 wheat protein hydrolysate 0.2 silica 0.1 triazene of Example36 4.88 coupler of Example 36 4.79 water ad 100

After contact for 30 minutes, without being washed out, a dye mixtureknown from U.S. Pat. No. 6,248,314 and having the following composition:Black Color No. 401 0.1 Purple Color 401 0.05 Orange Color No. 205 0.1benzyl alcohol 2.0 ethylene carbonate 10 propylene carbonate 15 ethanol10 lactic acid 3.5 sodium carbonate of pH 2.9 solution hydroxyethylcellulose 1.5 water ad 100is applied to the hair. The hair is then combed through thoroughly,whereupon its pH becomes about 3. Then, after a contact period of 15minutes, the hair is rinsed thoroughly with water and dried.

A strong, intense, striking red coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 81

A strand of blond undamaged human hair is coloured with 10 g of acomposition consisting of 5 g each of compositions A and B. CompositionsA B C D cetyl stearyl alcohol 11.00 11.00 11.00 11.00 oleth-5 5.0 5.05.0 5.0 oleic acid 2.5 2.5 2.5 2.5 stearic acid monoethanolamide 2.5 2.52.5 2.5 coconut fatty acid 2.5 2.5 2.5 2.5 monoethanolamide sodiumlauryl sulfate 1.7 1.7 1.7 1.7 1,2-propanediol 1.0 1.0 1.0 1.0 ammoniumchloride 0.5 0.5 0.5 0.5 EDTA, tetrasodium salt 0.2 0.2 0.2 0.2 perfume0.4 0.4 0.4 0.4 wheat protein hydrolysate 0.2 0.2 0.2 0.2 silica 0.1 0.10.1 0.1 2,5-diaminotoluene sulfate 0.7 4-amino-2-hydroxytoluene 0.52,5,6-triamino-4- 0.2 hydroxypyrimidine sulfate sodium sulfite 1.0ascorbic acid 0.5 triazene of Example 52 13.76 coupler of Example 52 4.4Basic Red 51 0.4 Ammonia (25%) 9.2 9.2 9.2 9.2 composition: pH 9.8 9.89.8 9.8 water ad 100 ad 100 ad 100 ad 100

The colouring mixture is allowed to act on the hair for 30 minutes atabout 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 15 minutes, the strand isrinsed thoroughly, shampooed and then dried.

A strong, intense, striking red coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 82

A strand of blond undamaged human hair is coloured with a mixture of 15g of 6% hydrogen peroxide solution and a composition consisting of 5 geach of compositions A, B and C according to Example 81.

The colouring mixture is allowed to act on the hair for 30 minutes atabout 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

A strong, intense, striking red violet coloration having good fastnessto washing and fastness to rubbing properties is obtained.

EXAMPLE 83

A strand of blond undamaged human hair is coloured with a mixture of 20g of 6% hydrogen peroxide solution and a composition consisting of 5 geach of compositions A, B, C and D according to Example 81.

The colouring mixture is allowed to act on the hair for 30 minutes atabout 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

A strong, intense, striking red violet coloration having good fastnessto washing and fastness to rubbing properties is obtained.

EXAMPLE 84

A strand of blond undamaged human hair is coloured with a mixture of 15g of 6% hydrogen peroxide solution and a composition consisting of 5 geach of compositions A, B and D according to Example 81.

The colouring mixture is allowed to act on the hair for 30 minutes atabout 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

A strong, intense, striking red coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 85

A strand of blond undamaged human hair is coloured with 15 g of acomposition consisting of 5 g each of compositions A, B and D accordingto Example 81.

The colouring mixture is allowed to act on the hair for 30 minutes atabout 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

A strong, intense, striking red coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 86

A strand of blond undamaged human hair is coloured with 15 g of acomposition consisting of 5 g each of compositions A, B and D accordingto Example 81.

The colouring mixture is allowed to act on the hair for 30 minutes atabout 22° C. 10 g of a shampoo with a pH value of 3 are then applied tothe strand and are massaged in. After contact for 5 minutes, the strandis rinsed thoroughly and then dried.

A strong, intense, striking red coloration having good fastness towashing and fastness to rubbing properties is obtained.

1. A method of colouring porous material, which method comprisesapplying to the material being coloured, in any desired ordersuccessively, or simultaneously, a) at least one capped diazoniumcompound of formula (1)

and/or at least one compound of formula (2)

and/or at least one compound of formula (3)

wherein Q is an unsubstituted or substituted aromatic or heterocyclicresidue, R is the radical of an unsubstituted or substituted,water-soluble aliphatic or aromatic amine, and T is an unsubstituted orsubstituted, water-soluble aliphatic or aromatic residue, wherein atleast one of the groups must contain a radical imparting watersolubility, and b) at least one water-soluble coupling component underconditions such that, initially, coupling does not take place, and thencausing the capped diazonium compound present on the material to reactwith the coupling component, with the provisos that (i) if thewater-soluble coupling component is

then the capped diazonium compounds is not

(ii) if the water-soluble coupling component is

then the capped diazonium compound is not

(iii) if the water-soluble coupling component is then the cappeddiazonium compound is not

(iv) if the water-soluble coupling component is

then the capped diazonium compound is not

(v) if the water-soluble coupling component is

then the capped diazonium compound is not

(vi) if the water-soluble coupling component is

then the capped diazonium compound is not

(vii) if the water-soluble coupling component is

then the capped diazonium compound is not

(viii) if the water-soluble coupling component is

then the capped diazonium compound is not

(ix) if the water-soluble coupling component is

then the capped diazonium compound is not

and (x) if the water-soluble coupling component is

then the diazonium capped compound is not


2. A method according to claim 1, which method comprises applying to thematerial being coloured, in any desired order successively, orsimultaneously, a) at least one capped diazonium compound of formula (1)

and/or at least one compound of formula (2)

and/or at least one compound of formula (3)

wherein Q is an unsubstituted phenyl; naphthyl; thiophenyl;1,3-thiazolyl; 1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl;imidazolyl; 1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl;pyrazolyl; benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl;pyrimidinyl; isoxazolyl; aminodiphenyl; aminodiphenylether andazobenzenyl or Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl,1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl andisoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl which ismono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio,halogen, nitro, trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl,phenylsulfonyl, benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or bydi-(hydroxy-C₁-C₄alkyl)-aminosulfonyl, R is a radical of formula—NR₁₆R₁₇, wherein R₁₆ is H; unsubstituted linear or branched C₁-C₆alkylor linear or branched C₁-C₆alkyl, which is substituted by one or moreidentical or different substituent selected from the group consisting ofOC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇is unsubstituted linear or branched C₁-C₆alkyl or linear or branchedC₁-C₆alkyl, which is substituted by one or more identical or differentsubstituent selected from the group consisting of OC₁-C₄alkyl, COOH,COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, or R is a radical ofunsubstituted aniline; the radical of unsubstituted aminonaphthalene;the radical of aniline or aminonaphthalene, wherein the phenyl or thenaphthyl ring is substituted by one or more identical or differentsubstituent selected from the group consisting of COOH, SO₃H, CN,halogen, SO₂C₁-C₂alkyl, unsubstituted linear or branched C₁-C₄alkyl,linear or branched C₁-C₄alkyl, substituted by OH, carboxy, COC₁-C₂alkylor SO₂—N(C₁-C₄alkyl)-(CH₂)₁₋₄SO₃H and wherein the amino radical issubstituted by H, unsubstituted linear or branched C₁-C₄alkyl or linearor branched C₁-C₄alkyl, substituted by OH or carboxy, T is a linear orbranched unsubstituted C₁-C₆alkyl or linear or branched C₁-C₆alkyl,which is substituted by one or more identical or different substituentselected from the group consisting of OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl,SO₃H, NH₂, NH(C₁-C₂alkyl), N(C₁-C₂alkyl)₂, CN, halogen and OH, or T isunsubstituted phenyl; unsubstituted naphthyl; phenyl or naphthyl, whichare substituted by one or more identical or different substituentsselected from the group consisting of OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl,SO₃H, NH₂, NH(C₁-C₂alkyl), N(C₁-C₂alkyl)₂, CN, halogen and OH, and b) atleast one water-soluble coupling component under conditions such that,initially, coupling does not take place, and then causing the cappeddiazonium compound present on the material to react with the couplingcomponent, wherein the same provisos as in claim 1 apply.
 3. A methodaccording to claim 1, which method comprises applying to the materialbeing coloured, in any desired order successively, or simultaneously, a)at least one capped diazonium compound of formula (1)

and/or at least one compound of formula (2)

and/or at least one compound of formula (3)

wherein Q is an unsubstituted phenyl; naphthyl; thiophenyl;1,3-thiazolyl; 1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl;imidazolyl; 1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl;pyrazolyl; benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl;pyrimidinyl; isoxazolyl; aminodiphenyl; aminodiphenylether andazobenzenyl or Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl,1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl andisoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl which ismono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio,halogen, nitro, trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl,phenylsulfonyl, benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or bydi-(hydroxy-C₁-C₄alkyl)-aminosulfonyl, R is a radical of formula—NR₁₆R₁₇, wherein R₁₆ is H; unsubstituted linear or branched C₁-C₆alkylor linear or branched C₁-C₆alkyl, which is substituted by one or moreidentical or different substituent selected from the group consisting ofOC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇is unsubstituted linear or branched C₁-C₆alkyl or linear or branchedC₁-C₆alkyl, which is substituted by one or more identical or differentsubstituent selected from the group consisting of OC₁-C₄alkyl, COOH,COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, T is a linear or branchedC₁-C₆alkyl, which is substituted by one or two identical or differentsubstituent selected from the group consisting of COOH, SO₃H, NH₂,NH(C₁-C₂alkyl) and N(C₁-C₂alkyl)₂, or T is unsubstituted phenyl;unsubstituted naphthyl; phenyl or naphthyl, which are substituted by oneor more identical or different substituents selected from the groupconsisting of OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂,NH(C₁-C₂alkyl), N(C₁-C₂alkyl)₂, CN, halogen and OH, and b) at least onewater-soluble coupling component under conditions such that, initially,coupling does not take place, and then causing the capped diazoniumcompound present on the material to react with the coupling component,wherein the same provisos as in claim 1 apply.
 4. A method according toclaim 1, which method comprises applying to the material being coloured,in any desired order successively, or simultaneously, a) at least onecapped diazonium compound of formula (1)

wherein Q is an unsubstituted phenyl; naphthyl; thiophenyl;1,3-thiazolyl; 1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl;imidazolyl; 1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl;pyrazolyl; benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl;pyrimidinyl; isoxazolyl; aminodiphenyl; aminodiphenylether andazobenzenyl or Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl,1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl andisoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl which ismono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio,halogen, nitro, trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl,phenylsulfonyl, benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or bydi-(hydroxy-C₁-C₄alkyl)-aminosulfonyl, R is a radical of formula—NR₁₆R₁₇, wherein R₁₆ is H; unsubstituted linear or branched C₁-C₆alkylor linear or branched C₁-C₆alkyl, which is substituted by one or moreidentical or different substituent selected from the group consisting ofOC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇is unsubstituted linear or branched C₁-C₆alkyl or linear or branchedC₁-C₆alkyl, which is substituted by one or more identical or differentsubstituent selected from the group consisting of OC₁-C₄alkyl, COOH,COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and b) at least onewater-soluble coupling component under conditions such that, initially,coupling does not take place, and then causing the capped diazoniumcompound present on the material to react with the coupling component,wherein the same provisos as in claim 1 apply.
 5. A method according toclaim 1, wherein the coupling component is an unsubstituted orsubstituted acylacetarylamide, phenol, naphthol, pyridine, quinolone,pyrazole, indole, diphenylamine, aniline, aminopyridine, pyrimidone,naphthylamine, aminothiazole, thiophene or hydroxypyridine.
 6. A methodaccording to claim 5, wherein the coupling component is mono- orpoly-substituted by amino, alkylamino, dialkylamino, halogen, alkyl,alkoxy, phenyl, naphthyl or by aryloxy.
 7. A method according to claim1, which method comprises applying to the material being coloured, inany desired order successively, or simultaneously, a) at least onecapped diazonium compound of formula (1)

and/or at least one compound of formula (2)

and/or at least one compound of formula (3)

wherein Q is an unsubstituted phenyl; naphthyl; thiophenyl;1,3-thiazolyl; 1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl;imidazolyl; 1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl;pyrazolyl; benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl;pyrimidinyl; isoxazolyl; aminodiphenyl; aminodiphenylether andazobenzenyl or Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl,1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl andisoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl which ismono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio,halogen, nitro, trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl,phenylsulfonyl, benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or bydi-(hydroxy-C₁-C₄alkyl)-aminosulfonyl, R is a radical of formula—NR₁₆R₁₇, wherein R₁₆ is H; unsubstituted linear or branched C₁-C₆alkylor linear or branched C₁-C₆alkyl, which is substituted by one or moreidentical or different substituent selected from the group consisting ofOC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇is unsubstituted linear or branched C₁-C₆alkyl or linear or branchedC₁-C₆alkyl, which is substituted by one or more identical or differentsubstituent selected from the group consisting of OC₁-C₄alkyl, COOH,COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, T is a linear or branchedC₁-C₆alkyl, which is substituted by one or two identical or differentsubstituent selected from the group consisting of COOH, SO₃H, NH₂,NH(C₁-C₂alkyl) and N(C₁-C₂alkyl)₂, or T is unsubstituted phenyl;unsubstituted naphthyl; phenyl or naphthyl, which are substituted by oneor more identical or different substituents selected from the groupconsisting of OC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂,NH(C₁-C₂alkyl), N(C₁-C₂alkyl)₂, CN, halogen and OH, and b) at least onewater-soluble coupling component selected from the group consisting ofacylacetarylamides, phenols, naphthols, pyridones, quinolones,pyrazoles, indoles, diphenylamines, anilines, aminopyridines,pyrimidones, naphthylamines, aminothiazoles, thiophenes andhydroxypyridines, which all may carry further substituents selected fromthe group consisting of amino, alkylamino, dialkylamino, halogen, alkyl,alkoxy, aryl, aryloxy, hydroxy, carboxy and sulfo, under conditions suchthat, initially, coupling does not take place, and then causing thecapped diazonium compound present on the material to react with thecoupling component, wherein the same provisos as in claim 1 apply.
 8. Amethod according to claim 1, which method comprises applying to thematerial being coloured, in any desired order successively, orsimultaneously, a) at least one capped diazonium compound of formula (1)

wherein Q is an unsubstituted phenyl; naphthyl; thiophenyl;1,3-thiazolyl; 1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl;imidazolyl; 1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl;pyrazolyl; benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl;pyrimidinyl; isoxazolyl; aminodiphenyl; aminodiphenylether andazobenzenyl or Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl,1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl andisoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl which ismono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio,halogen, nitro, trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl,phenylsulfonyl, benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or bydi-(hydroxy-C₁-C₄alkyl)-aminosulfonyl, R is a radical of formula—NR₁₆R₁₇, wherein R₁₆ is H; unsubstituted linear or branched C₁-C₆alkylor linear or branched C₁-C₆alkyl, which is substituted by one or moreidentical or different substituent selected from the group consisting ofOC₁-C₄alkyl, COOH, COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and R₁₇is unsubstituted linear or branched C₁-C₆alkyl or linear or branchedC₁-C₆alkyl, which is substituted by one or more identical or differentsubstituent selected from the group consisting of OC₁-C₄alkyl, COOH,COOC₁-C₂alkyl, SO₃H, NH₂, CN, halogen and OH, and b) at least onewater-soluble coupling component selected from the group consisting ofacylacetarylamides, phenols, naphthols, pyridones, quinolones,pyrazoles, indoles, diphenylamines, anilines, aminopyridines,pyrimidones, naphthylamines, aminothiazoles, thiophenes andhydroxypyridines, which all may carry further substituents selected fromthe group consisting of amino, alkylamino, dialkylamino, halogen, alkyl,alkoxy, aryl, aryloxy, hydroxy, carboxy and sulfo, under conditions suchthat, initially, coupling does not take place, and then causing thecapped diazonium compound present on the material to react with thecoupling component, wherein the same provisos as in claim 1 apply.
 9. Amethod of colouring porous material according to claim 1, which methodcomprises applying to the material being coloured, in any desired ordersuccessively, or simultaneously, a) at least two capped diazoniumcompounds as defined in claim 1 and b) at least one water-solublecoupling component under conditions such that, initially, coupling doesnot take place, and then causing the capped diazonium compound presenton the material to react with the coupling component.
 10. A method ofcolouring porous material according to claim 1, which method comprisesapplying to the material being coloured, in any desired ordersuccessively, or simultaneously, a) at least one capped diazoniumcompound as defined in claim 1 and b) at least two water-solublecoupling components under conditions such that, initially, coupling doesnot take place, and then causing the capped diazonium compound presenton the material to react with the coupling component.
 11. A method ofcolouring porous material according to claim 1, which method comprisesapplying to the material being coloured, in any desired ordersuccessively, or simultaneously, a) at least two capped diazoniumcompounds as defined in claim 1 and b) at least two water-solublecoupling components under conditions such that, initially, coupling doesnot take place, and then causing the capped diazonium compound presenton the material to react with the coupling component.
 12. A methodaccording to claim 1, which method comprises bringing the material beingcoloured into contact with a) at least one capped diazonium compound asdefined in claim 1 and b) at least one water-soluble coupling component,in any desired order successively, or simultaneously, a) under alkalineconditions in the presence of an oxidising agent and optionally in thepresence of a further dye, and then subjecting the material beingcoloured to treatment with acid, or b) under alkaline conditions, andthen subjecting the material being coloured to treatment with acid,optionally in the presence of a further dye, wherein the same provisosas in claim 1 apply.
 13. A method according to claim 9, wherein thecoupling component is unsubstituted or substituted acylacetarylamide,phenol, naphthol, pyridine, quinolone, pyrazole, indole, diphenylamine,aniline, aminopyridine, pyrimidone, naphthylamine, aminothiazole,thiophene or hydroxypyridine.
 14. A method according to claim 13,wherein the coupling component is mono- or poly-substituted by amino,alkylamino, dialkylamino, halogen, alkyl, alkoxy, phenyl, naphthyl or byaryloxy.
 15. A compound of formula

wherein Q is an unsubstituted phenyl; naphthyl; thiophenyl;1,3-thiazolyl; 1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl;imidazolyl; 1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl;pyrazolyl; benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl;pyrimidinyl; isoxazolyl; aminodiphenyl; aminodiphenylether andazobenzenyl or Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl,1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl,1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl,benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl andisoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl which ismono- or poly-substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio,halogen, nitro, trifluoromethyl, CN, SCN, C₁-C₄alkylsulfonyl,phenylsulfonyl, benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl,C₁-C₄alkyl-carbonylamino, C₁-C₄alkoxysulfonyl or bydi-(hydroxy-C₁-C₄alkyl)-aminosulfonyl, R is radical of unsubstitutedaniline; the radical of unsubstituted aminonaphthalene; the radical ofaniline or aminonaphthalene, wherein the phenyl or the naphthyl ring issubstituted by one or more identical or different substituent selectedfrom the group consisting of COOH, SO₃H, CN, halogen, SO₂C₁-C₂alkyl,unsubstituted linear or branched C₁-C₄alkyl, linear or branchedC₁-C₄alkyl, substituted by OH, carboxy, COC₁-C₂alkyl orSO₂—N(C₁-C₄alkyl)-(CH₂)₁₋₄SO₃H and wherein the amino radical issubstituted by H, unsubstituted linear or branched C₁-C₄alkyl or linearor branched C₁-C₄alkyl, substituted by OH or carboxy, wherein thecompound of formula

is excluded.
 16. A colouring composition for carrying out the methodaccording to claim 1, comprising a) at least one compound of formula(1), (2) and/or (3) described in claim 1, b) a medium for adjusting thepH, c) water, and, optionally, d) further additives.
 17. A colouringcomposition according to claim 16, comprising a) at least one compoundof formula (1), (2) and/or (3), b) a medium for adjusting the pH, c)water, d) at least one coupling component, and, optionally, e) furtheradditives, with the provisos that (i) if the water-soluble couplingcomponent is

then the capped diazonium compound must not be

and (ii) if the water-soluble coupling component is

then the capped diazonium compound must not be


18. A colouring composition for carrying out the method according toclaim 17, comprising a) at least one compound of formula (1), (2) and/or(3), b) a medium for adjusting the pH, c) water, d) at least onewater-soluble coupling component selected from the group consisting ofacylacetarylamides, phenols, naphthols, pyridones, quinolones,pyrazoles, indoles, diphenylamines, anilines, aminopyridines,pyrimidones, naphthylamines, aminothiazoles, thiophenes andhydroxypyridines, which all may carry further substituents selected fromthe group consisting of amino, alkylamino, dialkylamino, halogen, alkyl,alkoxy, aryl, aryloxy, hydroxy, carboxy and sulfo and, optionally, e)further additives, wherein the same provisos as in claim 17 apply.
 19. Acolouring composition for carrying out the method according to claim 17,comprising a) at least one compound of formula (1), (2) and/or (3), b) amedium for adjusting the pH, c) water, d) at least one water-solublecoupling component selected from the group consisting ofacylacetarylamides, phenols, naphthols, pyridones, quinolones,pyrazoles, indoles, diphenylamines, anilines, aminopyridines,pyrimidones, naphthylamines, aminothiazoles, thiophenes andhydroxypyridines, which all may carry further substituents selected fromthe group consisting of amino, alkylamino, dialkylamino, halogen, alkyl,alkoxy, aryl, aryloxy, hydroxy, carboxy and sulfo, e) a further dyewhich is an oxidation dye, or a cationic, anionic or uncharged directdye and, optionally, f) further additives, wherein the same provisos asin claim 17 apply.